Strategies for Integrating Metal Nanoparticles with Two-Photon Polymerization Process: Toward High Resolution Functional Additive Manufacturing

This study reports the successful fabrication of complex 3D metal nanoparticle–polymer nanocomposites using two-photon polymerization (2PP). Three complementary strategies are detailed: in situ formation of metal nanoparticles (MeNPs) through a single-step photoreduction process, integration of pre-formed MeNPs into 2PP resin, and site-selective MeNPs decoration of 3D 2PP structures. In the in situ formation strategy, a phase-transfer method is applied to transfer silver and copper ions from an aqueous phase into a toluene solvent to disperse them in photoreactive monomers.The addition of a photosensitive dye, coumarin 30, facilitated the reduction of silver ions and improved the distribution of silver nanoparticles (AgNPs). This strategy is successfully used to produce other MeNPs, such as Cu and Au. The integration of pre-formed MeNPs enabled highly controlled NP size distribution within the 2PP 3D structures with high-fidelity To enable selective decoration of 2PP 3D surfaces with MeNPs, a multimaterial strategy is developed, with one of the resins designed for thiol-ene reaction, which demonstrated selective binding to AuNPs. The successful development of complementary strategies for integration of MeNPs into 2PP resins offers exciting opportunities for fabrication of MeNP composites with sub-micron resolution for applications from photonics to metamaterials and drug delivery.     

Extended H2 photoproduction by N2-fixing cyanobacteria immobilized in thin alginate films

Screening of the University of Helsinki Culture Collection for naturally good H₂ producing cyanobacteria recently revealed several promising strains. One of the superior strains is Calothrix 336/3, an N₂-fixing heterocystous filamentous cyanobacterium. Making use of an important feature of the Calothrix 336/3 cells to adhere to the substrate, we applied an immobilization technique to improve H₂ production capacity of this strain. We examined the basic properties of immobilization in Ca²⁺-alginate films in response to the production of H₂ of the Calothrix 336/3 strain and as reference strains we used a model organism Anabaena PCC 7120 and its uptake hydrogenase mutant, ΔhupL, that allow us to compare the responses of different strains to alginate entrapment. Immobilization of the Calothrix 336/3 and ΔhupL mutant cells in Ca²⁺-alginate resulted in prolonged H₂ production over several cycles. Immobilization of the Calothrix 336/3 cells was most successful and production of H₂ could be measured even after 40 days after immobilization.     

Hydrogen transport in single-walled carbon nanotubes encapsulated by palladium

Hydrogen transport and loading into single-walled carbon nanotubes (SWCNT) encapsulated by thin Pd layers onto a massive Pd substrate were studied using a complex of vacuum thermal desorption, cyclic voltammetry and ESR methods. By adding SWCNT the hydrogen capacity of the Pd–SWCNT composite under electrochemical loading increases as much as 25% relative to Palladium metal alone. This provides moderate growth in the gravimetric capacity of the total composite based on a massive Pd substrate. The hydrogen binding energy in the SWCNT (eH = 0.075 eV/H-atom), estimated by studies of hydrogen transport in the Pd–SWCNT composite was lower than predicted for the Pd–SWCNT complex, but higher than the physisorption on the bare SWCNT. Using ESR we established that the Pd–C_x e-complexes formed at the wall of nanotube could be considered as hydrogen adsorption site, providing both high net gravimetric capacity and low hydrogen binding energy in the Pd encapsulated SWCNT. The results obtained provide an opportunity to probe a condensed hydrogen phase of nanometer scale confined in SWCNT, encapsulated by transition metals.     

Effect of Boron on the Structure and Composition of Cobalt Silicides

The system Co ― Si ― B is promising for development of new soft magnetic materials. We studied the effect of boron on the structure and composition of cobalt silicides during solid-phase reaction of powders of the starting components under a 3·10^?3 Pa vacuum in the temperature range 200°C to 1300°C for boron content from 0.5 mass% to 7.7 mass% by differential thermal analysis, metallographic analysis, x-ray analysis, and electron-probe microanalysis. We established that boron is not soluble in cobalt silicides. Formation of ternary chemical compounds is typical for the Co ― Si ― B system.

     

Cationic and radical polymerization of N-vinyl-2-phenylpyrrole: Synthesis of electroconducting,paramagnetic and fluorescent oligomers

Cationic polymerization of N-vinyl-2-phenylpyrrole (catalysts: Me₃SiCl, CF₃COOH, BF₃·OEt₂, HCl, WCl₆, FeCl₃, complex LiBF₄–dimethoxyethane, catalysts concentration 1–2 wt%, 20–70 °C, 24–48 h) affords oligomers (molecular weight 1400–1700) of a unexpected structure with alternating 2-phenylpyrrole and ethylydene units, the yields reaching 63%. The oligomers structure has been supported by isolation and identification of the corresponding dimer, N-vinyl-2-phenyl-5-[N-(2-phenyl-1H-pyrrol-1-yl)ethyl]-1H-pyrrole. Radical polymerization of the same monomer (AIBN, 1.5–4 wt%, 60–80 °C, 40–60 h or UV irradiation or both) gives oligomers (molecular weight 2100–3000) of normal structure having polyethene backbone with pendant 2-phenylpyrrole groups in up to 40% yields. The oligomers of both types are semiconductors (1.3 × 10^?6–3.6 × 10^?6 S/cm) after doping with I₂, paramagnetic (4.2 × 10¹⁷–8.7 × 10¹⁷ g^?1) and fluorescent in a near UV region (λ 355–363 nm, acetonitrile).     

Preparation of Hard Alloy WC and WC – Co Mixtures with Reduction and Carbidizing Treatment of Oxidized Tungsten Containing Scrap

A method of single-stage reduction and carbidizing treatment of oxidized tungsten containing scrap (hard alloys of the VK type and tungsten wire) is proposed. Procedures are suggested for preparing very fine tungsten carbide of stoichiometric composition without adding carbon black by reduction and carbidizing treatment of oxidized tungsten wire scrap and also with introduction of solid carbon (carbon black) during reduction and carbidizing treatment of oxidized hard alloy scrap.     

Antimicrobial properties and thermal stability of polycarbonate modified with 1‐alkyl‐3‐methylimidazolium tetrafluoroborate ionic liquids

Four water immiscible ionic liquids (ILs): 1‐hexyl‐3‐methylimidazolium tetrafluoroborate, 1‐heptyl‐3‐methylimidazolium tetrafluoroborate, 1‐octyl‐3‐methylimidazolium tetrafluoroborate and 1‐dodecyl‐3‐methylimidazolium tetrafluoroborate have been synthesized. Polycarbonate (PC) films containing ILs were prepared by solvent casting from methylene chloride solutions. Scanning electron microscopy measurements showed the high homogeneity of PC/IL films with the IL content up to 4 wt %. The tendency to IL aggregation was observed for polymeric films with higher IL content (5%). PC/IL composites were found to have the reduced thermal decomposition temperature under both an air and a nitrogen atmosphere in comparison with the neat PC. The effect of IL content on the antimicrobial activity of PC films against Escherichia coli bacteria was studied. Pronounced antimicrobial efficacy was revealed for PC/IL films for all studied ILs starting from 3 wt % of IL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40050.     

Particle‐Based Optical Sensing of Intracellular Ions at the Example of Calcium – What Are the Experimental Pitfalls?

Colloidal particles with fluorescence read‐out are commonly used as sensors for the quantitative determination of ions. Calcium, for example, is a biologically highly relevant ion in signaling, and thus knowledge of its spatio‐temporal distribution inside cells would offer important experimental data. However, the use of particle‐based intracellular sensors for ion detection is not straightforward. Important associated problems involve delivery and intracellular location of particle‐based fluorophores, crosstalk of the fluorescence read‐out with pH, and spectral overlap of the emission spectra of different fluorophores. These potential problems are outlined and discussed here with selected experimental examples. Potential solutions are discussed and form a guideline for particle‐based intracellular imaging of ions.     

Structural Effects in Determining Silicon Concentration in Al - Si Alloys by X-Ray Fluorescence and Mass Spectrometry

The paper discusses how the structure of aluminum alloys affects the determination of silicon by x-ray fluorescence and glow-discharge mass spectrometry. As the silicon microcrystals enlarge, there tends to be an exaggeration of its content. The kinetics of the silicon-ion concentration change in the glow-discharge plasma show that cathode sputtering causes reconstruction of the surface layer. The processes are different for a binary alloy (with 3% silicon) as against multicomponent alloys. A method is proposed for diminishing the structural effect, which is based on preliminary treatment of the surface with microsecond pulse discharges, which results in a microcrystalline surface layer of thickness 20–50 µm. This suppresses the structural effects and provides reliable data on the silicon content.__________Translated from Poroshkovaya Metallurgiya, Nos. 3–4(442), pp. 106–112, March–April, 2005.     

Economically Alloyed Manganese-Containing Powder Structural Steels. Composition, Preparation Conditions, and Properties

The possibility of replacing nickel by manganese in Cu - Ni steels is studied. The physicomechanical properties, composition, and production conditions for manganese-containing steels sintered in hydrogen and converted gas are determined. It is established that they may replace standard steel grade PK40N2D2.__________Translated from Poroshkovaya Metallurgiya, Nos. 3–4(442), pp. 25–31, March–April, 2005.