Fabrication of biomimetic materials and scaffolds is usually a micro- or even nanoscale process; however, most testing and all manufacturing require larger-scale synthesis of nanoscale features. Here, we propose the utilization of naturally prefabricated three-dimensional (3D) spongin scaffolds that preserve molecular detail across centimeter-scale samples. The fine-scale structure of this collagenous resource is stable at temperatures of up to 1200°C and can produce up to 4 × 10–cm–large 3D microfibrous and nanoporous turbostratic graphite. Our findings highlight the fact that this turbostratic graphite is exceptional at preserving the nanostructural features typical for triple-helix collagen. The resulting carbon sponge resembles the shape and unique microarchitecture of the original spongin scaffold. Copper electroplating of the obtained composite leads to a hybrid material with excellent catalytic performance with respect to the reduction of p-nitrophenol in both freshwater and marine environments.
A holdfast is a root-or basal plate-like structure of principal importance that anchors aquatic sessile organisms, including sponges, to hard substrates. There is to date little information about the nature and origin of sponges' holdfasts in both marine and freshwater environments. This work, to our knowledge, demonstrates for the first time that chitin is an important structural component within holdfasts of the endemic freshwater demosponge Lubomirskia baicalensis. Using a variety of techniques (near-edge X-ray absorption fine structure, Raman, electrospray ionization mas spectrometry, Morgan-Elson assay and Calcofluor White staining), we show that chitin from the sponge holdfast is much closer to a-chitin than to b-chitin. Most of the three-dimensional fibrous skeleton of this sponge consists of spicule-containing proteinaceous spongin. Intriguingly, the chitinous holdfast is not spongin-based, and is ontogenetically the oldest part of the sponge body. Sequencing revealed the presence of four previously undescribed genes encoding chitin synthases in the L. baicalensis sponge. This discovery of chitin within freshwater sponge holdfasts highlights the novel and specific functions of this biopolymer within these ancient sessile invertebrates.
The paper is devoted to the structure and properties of the composite material based on multi-walled carbon nanotubes (MWCNTs) covered with pyrolytic iron and chromium. Fe/MWCNTs and Cr/MWCNTs nanocomposites have been prepared by the metal organic chemical vapor deposition (MOCVD) growth technique using iron pentacarbonyl and bis(arene)chromium compounds, respectively. Composites structures and morphologies preliminary study were performed using X-ray diffraction, scanning and transmission electron microscopy and Raman scattering. The atomic and chemical composition of the MWCNTs’ surface, Fe-coating and Cr-coating and interface—(MWCNTs surface)/(metal coating) were studied by total electron yield method in the region of near-edge X-ray absorption fine structure (NEXAFS) C1s, Fe2p and Cr2p absorption edges using synchrotron radiation of the Russian-German dipole beamline (RGBL) at BESSY-II and the X-ray photoelectron spectroscopy (XPS) method using the ESCALAB 250 Xi spectrometer and charge compensation system. The absorption cross sections in the NEXAFS C1s edge of the nanocomposites and MWCNTs were measured using the developed approach of suppressing and estimating the contributions of the non-monochromatic background and multiple reflection orders radiation from the diffraction grating. The efficiency of the method was demonstrated by the example of the Cr/MWCNT nanocomposite, since its Cr2p NEXAFS spectra contain additional C1s NEXAFS in the second diffraction order. The study has shown that the MWCNTs’ top layers in composite have no significant destruction; the MWCNTs’ metal coatings are continuous and consist of Fe3O4 and Cr2O3. It is shown that the interface between the MWCNTs and pyrolytic Fe and Cr coatings has a multilayer structure: a layer in which carbon atoms along with epoxy –C–O–C– bonds form bonds with oxygen and metal atoms from the coating layer is formed on the outer surface of the MWCNT, a monolayer of metal carbide above it and an oxide layer on top. The iron oxide and chromium oxide adhesion is provided by single, double and epoxy chemical binding formation between carbon atoms of the MWCNT top layer and the oxygen atoms of the coating, as well as the formation of bonds with metal atoms.
The samples of Ni-doped
bismuth magnesium tantalate pyrochlores
with the general formula Bi
1.4
(Mg
1–
x
Ni
x
)
0.7
Ta
1.4
O
6.3
(
x
= 0.3, 0.5, 0.7) were
obtained by solid-phase synthesis. The crystal structure of the pyrochlore
type (sp. gr.
Fd
3̅
m:2
) was
clarified by the Rietveld method on the basis of X-ray powder diffraction
data. The unit cell parameters increase with the decreasing nickel
content in the range from 10.5319(1) to 10.5391(1) Å. The electronic
state of atoms is established by the XPS method. According to XPS
analysis, bismuth atoms have an effective charge of +3, nickel atoms
+(2 + δ), and tantalum ions +(5 – δ). The coefficient
of thermal expansion of the lattice of the samples was calculated
from high-temperature X-ray structural measurements in the range of
−180 to 1050 °C. The average values of linear TECs α
in the temperature ranges of 30–570 and 600–1050 °C
are 5.1 × 10
–6
and 8.1 × 10
–6
°C
–1
, respectively. The monotonicity of the
change in the thermal expansion coefficient in the temperature range
from −100 to 1050 °C indicates the absence of phase transformations.
All samples are dielectric and exhibit high activation energies ∼2.0
eV, moderately high dielectric constants ∼24–28, and
tangent dielectric losses ∼0.002 at 1 MHz and 21 °C. The
electrical properties of the samples are described by a simple parallel
equivalent scheme. The chemical composition of the materials has little
effect on the polarizability of the medium or on the value of the
activation energy of the conductivity. Ionic processes in investigated
materials at frequencies 200–10
6
Hz and at temperatures
100–450 °C were not detected.
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