Thorsenmcintosh2275

The stabilization of supported nanoclusters is critical for different applications, including catalysis and plasmonics. Herein we investigate the impact of MoS2 grain boundaries (GBs) on the nucleation and growth of Pt NCs. The optimum atomic structure of the metal clusters is obtained using an adaptive genetic algorithm that employs a hybrid approach based on atomistic force fields and density functional theory. Our findings show that GBs stabilize the NCs up to a cluster size of nearly ten atoms, and with larger clusters having a similar binding to the pristine system. Notably, Pt monomers are found to be attracted to GB cores achieving 60% more stabilization compared to the pristine surface. Furthermore, we show that the nucleation and growth of the metal seeds are facile with low kinetic barriers, which are of similar magnitude to the diffusion barriers of metals on the pristine surface. The findings highlight the need to engineer ultrasmall NCs to take advantage of enhanced stabilization imparted by the GB region, particularly to circumvent sintering behavior for high-temperature applications.The synthesis of branched gold nanoparticles (AuNPs) with shape- and size-specific optical properties requires effective control of the particle formation mechanism using appropriate reducing agents and protective agents that prevent particle aggregation in solution. In this context, the heterogeneous synthesis of AuNPs using solid surfaces of graphene oxides and metal-organic frameworks has attracted much attention. These materials are characterized by their ability to immobilize and stabilize the particles grown on the surface without the need for additional protective agents. However, the shape- and size-selective synthesis of AuNPs using solid surfaces remains challenging. Herein, we report the shape-selective one-step synthesis of monodisperse branched AuNPs using a metal-macrocycle framework (MMF), a porous molecular crystal of PdII3-tris(phenylenediamine) macrocycle. Konpeito-Shaped branched AuNPs with uniform size were obtained on the surface of MMF by mixing HAuCl4·4H2O, L-ascorbic acid and MMF microcrystals. Spectroscopic and microscopic observations confirmed that MMF promoted the reduction of gold by its reductive activity as well as acted as a solid support to electrostatically immobilize the pseudo-seed particles for further growth on the crystal surface. In addition, the MMF also served as a substrate for in situ high-speed AFM imaging due to the effective immobilization of AuNPs on the surface, allowing direct visualization of the particle growth. Since the chemical structural features of MMF allow the growth of branched AuNPs via pseudo-seeding, this approach would provide new synthetic methods for obtaining a variety of gold nanostructures.A strategically designed electrodeposition method is proposed for the coating of p-type copper(i) oxide (Cu2O) channels for oxide thin film transistors. To date, conventional p-type oxide semiconductors have revealed a poor mobility and stability and this has obstructed the development of all oxide based logic devices. Furthermore, previous studies on p-type oxide transistors have been limited by the use of a typical planar type configuration. Our Cu2O electrodeposition method designed by incorporating Sb element promotes vertical alignment of the grain boundaries (GBs) and it perfectly coincides with the charge transport direction from the source to the drain in the vertical field effect transistors. These vertically aligned GBs are bundle type GBs and are likely to be ideal for vertical transistors with supreme electrical performances owing to the structurally suppressed grain boundary charge scattering. This alignment of the GBs in the electrodeposited Sb doped Cu2O (SbCu2O) also demonstrates a superior vehese p-type Cu2O transistors by interconnecting n-type IGZO transistors.Fluorine chemistry was demonstrated to show the importance of stretching the limits of chemical synthesis, oxidation state, and chemical bonding at ambient conditions. Thus far, the highest fluorine stoichiometry of a neutral first-row transition-metal fluoride is five, in VF5 and CrF5. Pressure can stabilize new stoichiometric compounds that are inaccessible at ambient conditions. Here, we attempted to delineate the fluorination limits of first-row transition metals at a high pressure through first-principles swarm-intelligence structure searching simulations. Besides reproducing the known compounds, our extensive search has resulted in a plethora of unreported compounds CrF6, MnF6, FeF4, FeF5, FeF6, and CoF4, indicating that the application of pressure achieves not only the fluorination limit (e.g., hexafluoride) but also the long-sought bulky tetrafluorides. Our current results provide a significant step forward towards a comprehensive understanding of the fluorination limit of first-row transition metals.Direct ink writing (DIW) of Pickering emulsions offers great potential for constructing on-demand objects. However, the rheological properties of fluid emulsions greatly undermines the shape fidelity and structural integrity of 3D-printed structures. We solve here these challenges and realize a new route towards complex constructs for actual deployment. A dynamic, supramolecular host-guest hydrogel based on poly(ethylene glycol) and α-cyclodextrin was synthesized in the continuous phase of cellulose nanocrystal-stabilized Pickering emulsions. The storage modulus of the obtained emulgels could reach up to ∼113 kPa, while being shear thinning and yielding precise printability. Diverse complex architectures were possible with high shape fidelity and structural integrity. The printed objects, for example a double-wall cylinder with 75 layers, demonstrated excellent dimensional stability (shrinkage of 7 ± 2% after freeze-drying). With the merits of a simple fabrication process and the high biocompatibility of all the components, the concept of dynamic supramolecular hydrogel-reinforced emulgels represent a potentially versatile route to construct new materials and structures VIA DIW for use in bioproducts and biomedical devices.Noncentrosymmetric superconductors are strong candidates for exploring intrinsic topological superconductivity. Here, we predict two new noncentrosymmetric superconductors SnVSe2 and PbVSe2 by a systematic first-principles study. These two compounds show good thermal and dynamic stabilities. Moreover, the band topology of both compounds is predicted to be nontrivial via Z2 calculation and slab models. We also investigate the electron-phonon interactions in SnVSe2 and PbVSe2, indicating the Tc of SnVSe2 and PbVSe2 without external pressure are predicted to be ∼1.18 K and ∼0.22 K, respectively. Furthermore, the results on pressure engineering in PbVSe2 imply that the Tc of PbVSe2 can be tuned to 2.39 K for enhanced contributions from Pb layers under pressure up to 6.4 GPa. This work may provide new platforms for probing spin-triplet paring and may help with designing and developing new metal-intercalated transition metal dichalcogenides.The notion of a "silent CO group" (effectively an infinitely heavy CO group) is introduced to enable energy-factored force fields to be estimated accurately for molecules where there are fewer ν(CO) frequencies than force constants in the force field (viz. underdetermined force fields). The symmetry classes of molecules covered are the Cs tricarbonyls (e.g. Fe(CO)3(diene) and fac-Re(CO)3(L-L)X), C2v tricarbonyls (e.g. mer-M(CO)3(L)3 M = Cr, Mo, W), C3v tetracarbonyls (e.g. ATG-017 datasheet Fe(CO)4(L)), C2v tetracarbonyls (e.g. cis-M(CO)4(L)2 and Fe(CO)4(L)) and C4v pentacarbonyls (e.g. M(CO)5(L) M = Cr, Mo, W and M(CO)5(X) M = Mn, Re). It is a relatively simple matter to extend the method to types of molecules not directly considered in this paper.Accelerating waste management requires the conversion of polymer waste to value-added materials through sustainable approaches. While depolymerised PET has been used as feedstock to produce metal-organic frameworks, this is the first report of the successful one-pot hydrothermal synthesis of the desirable UiO-66 topology through the judicious choice of reactants, modulators and reaction conditions.NASICON-type Na3Zr2Si2PO12 (NZSP) is supposed to be one of the best potential solid electrolytes with the characteristics of high ionic conductivity and safety for use in solid-state sodium batteries. Many methods have been used to enhance the ionic conductivity of NZSP, among which liquid phase sintering is a simple and rapid method. However, the transport mechanism of sodium ions in a NZSP electrolyte obtained by liquid phase sintering is not clear, and its application in solid-state batteries has not been confirmed. In this study, we synthesized NZSP with Na2SiO3 additives by liquid phase sintering to reduce the sintering temperature and improve the ionic conductivity. NZSP with 5 wt% Na2SiO3 (NZSP-NSO-5) achieves the highest ionic conductivity of 1.28 mS cm-1 and the lowest activation energy of 0.21 eV. Furthermore, the DFT study proves the Na+ diffusion mechanism and the decline in activation energy after addition. Lastly, the Na/Na3V2(PO4)3 battery with a Na2SiO3-added NZSP solid electrolyte exhibits a remarkably extended cycling capacity of 96.6% capacity retention after being cycled at 0.1 C 100 times. The liquid phase sintering with addition of low melting point salt compounds to electrolyte powder represents a rapid and straightforward technique for improving other ceramic electrolytes.Monitoring the expression level of the intracellular tumor suppressor gene p21 mRNA is essential to reveal the progress and prognosis of a tumor. Methods widely reported for the detection of p21 mRNA are the real-time polymerase chain reaction and Northern blot. However, these methods only detect mRNA in vitro and cannot realize the in situ monitoring of the p21 mRNA expression level in living cells. Additionally, the sensor for the real-time tracking and monitoring of the p21 mRNA location without the help of a transfection reagent in living cells is still limited. Herein, a novel sticky-flare was constructed for the dynamic monitoring of the temporal and spatial variations of p21 mRNA in living cells. The nanoprobe consists of AuNP, a recognition sequence modified with Cy5, and a thiol-modified DNA sequence. The thiol oligonucleotide strand could act partially complementary to the Cy5-modified oligonucleotide strand to form a double-stranded DNA linked to AuNP, resulting in the fluorescence quenching of Cy5 due to the energy transfer from Cy5 to the gold sphere. In the presence of p21 mRNA, the Cy5-modified recognition nucleic acid specifically bound to p21 mRNA to form a more stable double chain and escaped from the gold sphere, leading to the recovery of red fluorescence. Our method is better than other methods in its ability to quantify the spatial distribution and expression level of p21 mRNA in living cells and discriminate various tumor cell lines with different p21 mRNA expression levels by the naked eye. Particularly, the sticky-flare probe used in this assay could allow the visual evaluation of the tumor treatment effect and the determination of the tumor progression stage by enabling monitoring of the relative expression level of p21 mRNA in tumor cells after cisplatin treatment. The method reported here is accurate, reliable and needs no auxiliary tools (transfection reagent), and thereby provides a promising route for the prognostic evaluation and drug development of cancer treatment in the future.