Graphene bimetallic-like cantilevers: probing graphene/substrate interactions

The remarkable mechanical properties of graphene, the thinnest, lightest, and strongest material in existence, are desirable in applications ranging from composite materials to sensors and actuators. Here, we demonstrate that these mechanical properties are strongly affected by the interaction with the substrate onto which graphene is deposited. By measuring the temperature-dependent deflection of graphene/substrate "bimetallic" cantilevers we determine strain, thermal expansion coefficient, and the adhesion force acting on graphene films attached to a substrate. Graphene deposited on silicon nitride (SiN(x)) is under much larger strain, ε(g) ～ 1.5 × 10(-2), compared to graphene on gold (Au), ε(g) < 10(-3). The thermal expansion coefficient α(g) of graphene attached to SiN(x) is found to be negative, in the range from (- 5... - 1) × 10(-6)K(-1) and smaller in magnitude than α(g) of suspended graphene. We also estimate the interfacial shear strength of the graphene/SiN(x) interface to be ～1 GPa at room temperature.     

Phase transition on the Si(001) clean surface prepared in UHV MBE chamber: a study by high-resolution STM and <Emphasis Type="Italic">in situ</Emphasis> RHEED

The Si(001) surface deoxidized by short annealing at T ~ 925°C in the ultrahigh vacuum molecuar beam epitaxy chamber has been in situ investigated using high-resolution scanning tunneling microscopy (STM)and redegreesected high-energy electron diffraction (RHEED. RHEED patterns corresponding to (2 × 1) and (4 × 4) structures were observed during sample treatment. The (4 × 4) reconstruction arose at T ≲ 600°C after annealing. The reconstruction was observed to be reversible: the (4 × 4) structure turned into the (2 × 1) one at T ≳ 600°C, the (4 × 4) structure appeared again at recurring cooling. The c (8 × 8) reconstruction was revealed by STM at room temperature on the same samples. A fraction of the surface area covered by the c (8 × 8) structure decreased, as the sample cooling rate was reduced. The (2 × 1) structure was observed on the surface free of the c (8 × 8) one. The c (8 × 8) structure has been evidenced to manifest itself as the (4 × 4) one in the RHEED patterns. A model of the c (8 × 8) structure formation has been built on the basis of the STM data. Origin of the high-order structure on the Si(001) surface and its connection with the epinucleation phenomenon are discussed.     

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

This article presents a general approach to solving the urgent practical problem of separation of 4f-(lanthanides, Ln³⁺) and 5f-elements (actinides, An³⁺) very similar in properties based on the DFT quantum-chemical supercomputer simulation of Ln³⁺ and An³⁺ complexes with polydentate nitrogen-containing heterocyclic ligands. The method allows to calculate the geometry parameters of ligands and complexes and the metal to ligand binding energies with accuracy, permitting a direct comparison of calculation results with the experimental data, and estimate selectivity factors for separation of Eu³⁺/Am³⁺ model pair cations (SF_Am/Eu) in extraction experiments on a semi-quantitative level.

The applicability of the method and the approach demonstrated by DFT-modeling (nonempirical PBE functional, extended relativistic full-electron basis set) of a large series of diamides of pyridine-2,6-dicarboxylic (dipicolinic) acid (L) with different substituents at the amide nitrogen atoms and in the pyridine cycle, as well as their complexes [LM]³⁺, (H₂O)_nM(NO₃)₃ (n = 3, 4), and LM(NO₃)₃ (M = Eu, Am).

Based on the theoretical analysis a new model is proposed that describes the mechanism of Ln³⁺ and An³⁺ extraction in two-phase system highly acidic water solution-organic solvent, according to which the formation of An³⁺ and Ln³⁺ complexes occurs at the water/organic interface as a substitution reaction of hydroxonium ion in a cavity of a protonated ligand for the metal cation.

Calculation results confirm the experimentally established higher extraction ability of dipicolinic acid diamides containing one aryl and one alkyl substituent at the amide nitrogen atoms compared to the N,N,N′,N′-tetraalkyl diamides (“effect of anomalous aryl strengthening”). Based on the simulation results the structure of the modified ligand L suggested that it should ensure maximum An³⁺/Ln³separation selectivity in the series of dipicolinic acid diamides.     

Metal silicide/poly-Si Schottky diodes for uncooled microbolometers

Nickel silicide Schottky diodes formed on polycrystalline Si 〈P〉 films are proposed as temperature sensors of monolithic uncooled microbolometer infrared focal plane arrays. The structure and composition of nickel silicide/polycrystalline silicon films synthesized in a low-temperature process are examined by means of transmission electron microscopy. The Ni silicide is identified as a multi-phase compound composed of 20% to 40% of Ni₃Si, 30% to 60% of Ni₂Si, and 10% to 30% of NiSi with probable minor content of NiSi₂ at the silicide/poly-Si interface. Rectification ratios of the Schottky diodes vary from about 100 to about 20 for the temperature increasing from 22℃ to 70℃; they exceed 1,000 at 80 K. A barrier of around 0.95 eV is found to control the photovoltage spectra at room temperature. A set of barriers is observed in photo-electromotive force spectra at 80 K and attributed to the Ni silicide/poly-Si interface. Absolute values of temperature coefficients of voltage and current are found to vary from 0.3%℃ to 0.6%/℃ for forward bias and around 2.5%/℃ for reverse bias of the diodes.     

3D Printing to Increase the Flexibility of the Chemical Synthesis of Biologically Active Molecules: Design of On-Demand Gas Generation Reactors

The development of new drugs is accelerated by rapid access to functionalized and D-labeled molecules with improved activity and pharmacokinetic profiles. Diverse synthetic procedures often involve the usage of gaseous reagents, which can be a difficult task due to the requirement of a dedicated laboratory setup. Here, we developed a special reactor for the on-demand production of gases actively utilized in organic synthesis (C₂H₂, H₂, C₂D₂, D₂, and CO₂) that completely eliminates the need for high-pressure equipment and allows for integrating gas generation into advanced laboratory practice. The reactor was developed by computer-aided design and manufactured using a conventional 3D printer with polypropylene and nylon filled with carbon fibers as materials. The implementation of the reactor was demonstrated in representative reactions with acetylene, such as atom-economic nucleophilic addition (conversions of 19–99%) and nickel-catalyzed S-functionalization (yields 74–99%). One of the most important advantages of the reactor is the ability to generate deuterated acetylene (C₂D₂) and deuterium gas (D₂), which was used for highly significant, atom-economic and cost-efficient deuterium labeling of S,O-vinyl derivatives (yield 68–94%). Successful examples of their use in organic synthesis are provided to synthesize building blocks of heteroatom-functionalized and D-labeled biologically active organic molecules.     

Reactive,nonreactive, and flash spark plasma sintering of Al2O3/SiC composites—A comparative study

The influence of different SPS-based methods, that is, conventional spark plasma sintering (SPS), flash SPS (FSPS), and reactive SPS (RSPS) on the properties of Al₂O₃/SiC composite was investigated. It was shown that the application of preliminary high energy ball milling of the powders significantly enhances the sinterability of the ceramics. It was also demonstrated that FSPS provides unique conditions for rapid, that is, less than a minute, consolidation of refractory ceramics. The Al₂O₃-20 wt% SiC composite produced by FSPS possesses the highest relative density (~99%), fracture toughness (7.5 MPa m^1/2), hardness (20.3 GPa) and wear resistance among all ceramics produced by other SPS-based approaches with dwelling time 10 minutes. The RSPS ceramics hold the highest Young's modulus (390 GPa). Substitution of micron-sized Al₂O₃ particles by nano alumina does not lead to measurable enhancement of the mechanical properties.     

Chitosan-based fiber-sponge materials as a promising tool for microalgae harvesting from Lake Baikal

Mass eutrophication of microalgae and cyanobacteria is observed in Lake Baikal in the past decade. In this paper, the concept of replaceable adsorption filter material based on chitosan flocculant filler and chlorinated polyvinyl chloride polymer nonwoven material are proposed. Functional and mechanical properties and morphology of the material are investigated depending on a packing density and a degree of chitosan filling. The introduction of 45% chitosan increases the Young's modulus up to 10 times, and it makes the material more rigid in 2.8 times. The high efficiency of sorption and growth inhibition of cumulative biomass culture was shown. The biomass source is taken from the coast of Barguzinsky Bay of Lake Baikal. Dominant species is microalgae of Scenedesmus genus.     

Pulsed laser reshaping and fragmentation of upconversion nanoparticles — from hexagonal prisms to 1D nanorods through “Medusa”-like structures

One dimensional (1D) nanostructures attract considerable attention, enabling a broad application owing to their unique properties. However, the precise mechanism of 1D morphology attainment remains a matter of debate. In this study, ultrafast picosecond (ps) laser-induced treatment on upconversion nanoparticles (UCNPs) is offered as a tool for 1D-nanostructures formation. Fragmentation, reshaping through recrystallization process and bioadaptation of initially hydrophobic (β-Na_1.5Y_1.5F₆: Yb³⁺, Tm³⁺/β-Na_1.5Y_1.5F₆) core/shell nanoparticles by means of one-step laser treatment in water are demonstrated. “True” 1D nanostructures through “Medusa”-like structures can be obtained, maintaining anti-Stokes luminescence functionalities. A matter of the one-dimensional UCNPs based on direction of energy migration processes is debated. The proposed laser treatment approach is suitable for fast UCNP surface modification and nano-to-nano transformation, that open unique opportunities to expand UCNP applications in industry and biomedicine.

     

Synthesis and surface properties of amphiphilic fluorine-containing diblock copolymers

Amphiphilic diblock copolymers (DCs) of 2,3,4,5,6-pentafluorostyrene (PFS) and 2-hydroxyethyl methacrylate (HEMA) of different composition and molecular weights were prepared by two-step reversible addition–fragmentation chain transfer (RAFT) polymerization and first used for preparation of superhydrophobic coatings for cotton/polyester fabrics. The transition from hydrophobic to superhydrophobic coatings is controlled by the ratio between poly(2,3,4,5,6-pentafluorostyrene) (PPFS) block and poly(2-hydroxyethyl methacrylate) (PHEMA) block lengths (P_n^PFS/P_n^HEMA). The increase in P_n^PFS/P_n^HEMA is accompanied by a significant increase in water (θ^Н₂^О) and diiodomethane (θ^CH₂^I₂) contact angles, which reach the plateau at P_n^PFS/P_n^HEMA = 3.5 and remains almost constant up to P_n^PFS/P_n^HEMA = 6.2. Surface modification of the cotton/polyester fabric with the DC having P_n^PFS/P_n^HEMA = 6.2 produced superhydrophobic surface with θ^Н₂^О = 158 ± 4° and contact angle hysteresis CAH = 5 ± 2°, and θ^CH₂^I₂ = 107 ± 3°.