Mssbauer study of Се2Fe17 compound in different magnetic states

Mssbauer spectra of two samples of the Ce2Fe17 compound have been analyzed and hyperfine parameters, compared. The samples were subjected to different preparation techniques and display different magnetic properties. It is established that to well fit the Mssbauer spectra of these samples, an appropriate model should be used that takes into account an additional subspectrum differing in hyperfine parameters from the subspectra employed in conventional models. It is shown that in the ferromagnetic state, the samples contain local regions with an antiferromagnetic order, the volume fraction of which, being different for two samples, increases on approaching the temperature of ferro-to-antiferromagnet transition

Photoinduced dynamics of oxyluciferin analogues: Unusual enol "super"photoacidity and evidence for keto-enol isomerization

International audienceThe first systematic pico-nanosecond time-resolved spectroscopic study of the firefly emitter oxyluciferin and two of its chemically modified analogues revealed that in the excited state the enol group is more acidic than the phenol group. The 6'-dehydroxylated derivative, in which only the 4-enolic hydroxyl proton is acidic, has an experimentally determined pK a* of 0.9 in dimethyl sulfoxide and an estimated pK a* of -0.3 in water. Moreover, this compound provided direct evidence that in a nonpolar, basic environment the keto form in the excited state can tautomerize into the enol, which subsequently undergoes excited-state proton transfer (ESPT) to produce enolate ion. This observation presents the first experimental evidence of excited-state keto-enol tautomerization of a firefly fluorophore, and it could be important in resolving the enol-keto conundrum related to the color-tuning mechanism of firefly bioluminescence. The 6'-dehydroxylated form of oxyluciferin adds a very rare case of a stable enol to the family of "super"photoacids. Cop. 2012 American Chemical Society

Photoinduced Dynamics of Oxyluciferin Analogues: Unusual Enol “Super”photoacidity and Evidence for Keto–Enol Isomerization

The first systematic pico-nanosecond time-resolved spectroscopic study of the firefly emitter oxyluciferin and two of its chemically modified analogues revealed that in the excited state the enol group is more acidic than the phenol group. The 6′-dehydroxylated derivative, in which only the 4-enolic hydroxyl proton is acidic, has an experimentally determined p<i>K</i>_a* of 0.9 in dimethyl sulfoxide and an estimated p<i>K</i>_a* of −0.3 in water. Moreover, this compound provided direct evidence that in a nonpolar, basic environment the keto form in the excited state can tautomerize into the enol, which subsequently undergoes excited-state proton transfer (ESPT) to produce enolate ion. This observation presents the first experimental evidence of excited-state keto–enol tautomerization of a firefly fluorophore, and it could be important in resolving the enol–keto conundrum related to the color-tuning mechanism of firefly bioluminescence. The 6′-dehydroxylated form of oxyluciferin adds a very rare case of a stable enol to the family of “super”photoacids

Ag-Nanowire Bundles with Gap Hot Spots Synthesized in Track-Etched Membranes as Effective SERS-Substrates

This paper presents a cost-effective approach for the template-assisted electrodeposition fabrication of substrates for surface-enhanced Raman scattering (SERS) with metal nanowires (NWs) grown in pores of polymer track-etched membranes (TM). This technique allows the synthesis of NWs array with its certain surface density and diameter (from dozen to hundreds of nm). NWs length also may be varied (order of μm) by controlling deposition time. Here we grow vertical Ag-NWs which are leaning towards their nearest neighbors, forming self-assembled bundles whose parameters depend on the NW aspect ratio (length to diameter). We show that in such bundles there are “hot spots” in the nm-gaps between NWs tips. Computer simulations have demonstrated a strong enhancement of the electric field within these hot spots; thus, the Raman signal is markedly amplified for analyte molecules placed directly inside the gaps. We have experimentally proved the potential of this SERS-technique on the example of 4-Mercaptophenylboronic acid (4-MPBA). For 4-MPBA the maximal enhancement of Raman signal was found at NWs length of ~1.6 μm and diameter of ~100 nm. The effect is higher (up to twice) if “wet” substrate is used just immediately after the TM polymer removal so that the tips are brought to lean after analyte exposure. We suggest this new type of nanostructured SERS-substrates as a base of effective sensing of extremely low concentration of analytes

Crystal structure of (2E,4E)-5-[bis(2-hydroxyethyl)amino]-1-(4-chlorophenyl)-5-phenylpenta-2,4-dien-1-one

In the title compound, C21H22ClNO3, the pentadiene unit is nearly planar [maximum deviation = 0.023 (1) Å], but the carbonyl O atom deviates significantly [by 0.304 (1) Å] from its mean plane, which is twisted with respect to the phenyl and chlorobenzene rings by 71.34 (13) and 46.40 (13)°, respectively. In the crystal, inversion-related molecules are linked by two pairs of O—H...O hydrogen bonds, forming chains propagating along [01-1], enclosing R22(16) and R22(22) ring motifs. The chains are linked via C—H...O hydrogen bonds and C—H...π interactions into a three-dimensional supramolecular architecture

Mssbauer study of Се2Fe17 compound in different magnetic states

Mssbauer spectra of two samples of the Ce2Fe17 compound have been analyzed and hyperfine parameters, compared. The samples were subjected to different preparation techniques and display different magnetic properties. It is established that to well fit the Mssbauer spectra of these samples, an appropriate model should be used that takes into account an additional subspectrum differing in hyperfine parameters from the subspectra employed in conventional models. It is shown that in the ferromagnetic state, the samples contain local regions with an antiferromagnetic order, the volume fraction of which, being different for two samples, increases on approaching the temperature of ferro-to-antiferromagnet transition

Keto or Enol-That is the Question: Recent Progress in Spectra-Structure Correlations of Firefly Oxyluciferin and its Derivatives

International audienc

Variation of Surface Nanostructures on (100) PbS Single Crystals during Argon Plasma Treatment

The nanostructuring of the (100) PbS single crystal surface was studied under varying argon plasma treatment conditions. The initial PbS single crystals were grown by high-pressure vertical zone melting, cut into wafer samples, and polished. Subsequently, the PbS single crystals were treated with inductively coupled argon plasma under varying treatment parameters such as ion energy and sputtering time. Plasma treatment with ions at a minimum energy of 25 eV resulted in the formation of nanotips with heights of 30–50 nm. When the ion energy was increased to 75–200 eV, two types of structures formed on the surface: high submicron cones and arrays of nanostructures with various shapes. In particular, the 120 s plasma treatment formed specific cruciform nanostructures with lateral orthogonal elements oriented in four directions. In contrast, plasma treatment with an ion energy of 75 eV for 180 s led to the formation of submicron quasi-spherical lead structures with diameters of 250–600 nm. The nanostructuring mechanisms included a surface micromasking mechanism with lead formation and the vapor–liquid–solid mechanism, with liquid lead droplets acting as self-forming micromasks and growth catalysts depending on the plasma treatment conditions (sputtering time and rate)

Variation of Surface Nanostructures on (100) PbS Single Crystals during Argon Plasma Treatment

The nanostructuring of the (100) PbS single crystal surface was studied under varying argon plasma treatment conditions. The initial PbS single crystals were grown by high-pressure vertical zone melting, cut into wafer samples, and polished. Subsequently, the PbS single crystals were treated with inductively coupled argon plasma under varying treatment parameters such as ion energy and sputtering time. Plasma treatment with ions at a minimum energy of 25 eV resulted in the formation of nanotips with heights of 30&ndash;50 nm. When the ion energy was increased to 75&ndash;200 eV, two types of structures formed on the surface: high submicron cones and arrays of nanostructures with various shapes. In particular, the 120 s plasma treatment formed specific cruciform nanostructures with lateral orthogonal elements oriented in four &lt;100&gt; directions. In contrast, plasma treatment with an ion energy of 75 eV for 180 s led to the formation of submicron quasi-spherical lead structures with diameters of 250&ndash;600 nm. The nanostructuring mechanisms included a surface micromasking mechanism with lead formation and the vapor&ndash;liquid&ndash;solid mechanism, with liquid lead droplets acting as self-forming micromasks and growth catalysts depending on the plasma treatment conditions (sputtering time and rate)

Novel synthesis and properties of hydrogen-free detonation nanodiamond

Practically hydrogen-free nanodiamond (HFND), a prospective neutron-optical material, was prepared (in up to 3% yield) by detonating pure or graphite-doped RDX in an ice shell and comprehensively characterized by elemental analysis, X-ray diffraction, TEM, SAED, EELS, Raman and IR spectra, ESR, DSC/TGA, and specific-surface (BET) determination. The primary diamond grains are larger (15–16 nm) than in ordinary nanodiamond from RDX/TNT blends (ca. 5 nm) but smaller than in HFND from benzotrifuroxan (27 nm), with electron spins distributed in volume. HFND is much less hygroscopic and more prone to oxidation than ordinary nanodiamond. When heated in air up to 400°С, HFND shown a drastic increase of oxygen/carbon ratio without an apparent loss of mass. The mechanism of hydrogen non-contamination (through segregation of detonation gases) and particle growth is discussed