In-situ formation and detailed analysis of imine bonds for the construction of conjugated aromatic monolayers on Au(111)

We present the synthesis of 4′-amino-4-mercaptobiphenyl (AMB) and its deposition from solution onto Au(111) substrates. The resulting organic thin films were characterized by contact angle, infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure (NEXAFS) measurements. It is demonstrated that the majority of AMB molecules are coupled to the gold surface via S–Au covalent bonds, although only little orientational order of the AMB layer could be detected by NEXAFS. Furthermore, aromatic imine bonds between AMB and 4-hydroxybenzaldehyde (HB), 4-carboxybenzaldehyde (CB), 4-methylbenzaldehyde (MB), or 4-(trifluoromethyl) benzaldehyde (TMB) have been successfully formed. As a result of the limited order, this coupling reaction was incomplete. Nevertheless, the experimental results confirmed the formation of conjugated aromatic imine bonds.     

Synthesis and Reactivity of Mg(II)–Fe(II)–Fe(III) Hydroxycarbonates

Green rust-like compounds (GRs) were discovered as natural minerals in various hydromorphic soils, where anoxic conditions allow their stability. They may control some redox processes in aquifers and participate to the transformation of various pollutants. Since Mg(II) cations are present in the fields where GRs were discovered, a partial substitution of Mg(II) to Fe(II) leading to intermediate compounds between GRs and usual Mg(II)–Fe(III) hydroxysalts is suspected. Mg(II)–Fe(II)–Fe(II) hydroxycarbonates can be obtained as intermediate oxidation products of (Mg, Fe)(OH)₂ in carbonate-containing aqueous media obeying to [Fe^II _4(1–x)Mg^II _4x Fe^III ₂(OH)₁₂]²⁺ [CO₃ ^2– nH₂O]^–2. TMS spectra at 12 K are similar to those of GRs, i.e., two quadrupole doublets, one due to Fe(II) with a large isomer shift =1.29 mms^–1 (with respect to -iron at room temperature) and quadrupole splitting E _Q=2.76 mms^–1, the other one due to Fe(III) with smaller hyperfine parameters =0.49 mms^–1 and E _Q=0.44 mms^–1. Fe(II) ions oxidise rapidly into Fe(III) with dissolved O₂. The reactivity is similar to that of Fe(II)–Fe(III) hydroxysalts GR, and thus the potential of Mg(II)–Fe(II)–Fe(III) compounds for reducing pollutants.     

Infrared Photoreflectance of III–V Semiconductor Materials (Review)

Physics of the Solid State - The photoreflectance method, i.e., a contactless version of optical modulation spectroscopy is applied to the study of the band structure features of single-crystal...     

Spin distribution factors for formation of metastable states of 90Y and 91Y through (n,p) reactions over neutron energies 5–15 MeV

The variations in the isomer ratio with the spin distribution factor were studied to obtain the cross-sections for formation of metastable states of ⁹⁰Y and ⁹¹Y nuclei formed respectively through ⁹⁰Zr(n,p)⁹¹Y^m and ⁹¹Zr(n,p)⁹¹Y^m reactions over the neutron energy range 5 to 15 MeV. The theoretical values of the cross-sections could be obtained very close to the respective literature experimental values by varying the spin distribution factor from 1.5 to 2.75. The limiting value of the cross-section was derived from the maximum value of the isomer ratio at that neutron energy, and for this the spin distribution factor was found to vary from 2 to 3.5 over the neutron energies 5 to 15 MeV. Using enriched zirconium targets, cross-sections for formation of ⁹⁰Y^m and ⁹¹Y^m nuclei at 14.8 MeV neutron energy were also measured in the laboratory; the values obtained are 17 ± 2 mb and 22 ± 2 mb respectively for ⁹⁰Y^m and ⁹¹Y^m. Both these values are close to the corresponding limiting cross-sections at 14 MeV neutron energy.     

Progress on the natural asphalt applications as a new class of carbonious heterogeneous support; synthesis of Na[Pd-NAS] and study of its catalytic activity in the formation of carbon–carbon bonds

Molecular Diversity - In continuation of our recent research on introducing natural asphalt as a new carbonious, eco-friendly, highly economical support, and also in addition to our plan to develop...     

Studies on the σ–hole bonds (halogen,chalcogen, pnicogen and carbon bonds) based on the orientation of crystal structure

ABSTRACT

The 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole (DDBT) crystal has two polymorphic forms [1 M.S. Pavan, A.K. Jana, S. Natarajan, and T.N. Guru Row, J. Phys. Chem. B 119, 11382 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], where the close contacts between two electronegative atoms are identified and studied through Hirshfeld surface analysis. Br---Br and O---O cut-off distances are addressed and analysed. The σ–hole of bromine, sulphur, oxygen atoms and π-hole of carbon and nitrogen atoms were subjected to study using molecular electrostatic potential map and 3D-deformation density map. Sixteen types of dimers from the two forms of crystal structure (6 for form I and 10 for form II) were studied using the charge transfer properties and interaction energies and made detailed analysis of halogen bond (Br---N), dihalogen bond (Br---Br), chalcogen bond (O---Br and S---Br), dichalcogen bond (S---O, O---S and O---O), pnicogen bond (N---O) and carbon bond (C---O and C---Br) interactions. The impact of orientations is discussed to define the type of interaction and its strength through charge transfer mechanism. The contribution of bond angle values for the σ-hole and π–hole bonds are discussed. Utilisation of σ–hole in smaller bond angle values (above 30°) of |θ₁ ? θ₂| existing in type II halogen–halogen bond have been examined in the two forms.     

Darcy–Forchheimer 3D flow of carbon nanotubes with homogeneous and heterogeneous reactions

This article deals with Darcy–Forchheimer three dimensional (3D) flow of water-based carbon nanotubes (CNTs) with heterogeneous–homogeneous reactions. A bidirectional nonlinear extendable surface has been employed to create the flow. Flow in porous space is represented by Darcy–Forchheimer expression. Heat transfer mechanism is explored through convective heating. Equal diffusion coefficients are considered for both auto catalyst and reactants. Results for single-wall (SWCNT) and multi-wall (MWCNT) carbon nanotubes have been presented and compared. The diminishment of partial differential framework into nonlinear ordinary differential framework is made through suitable transformations. Optimal homotopy scheme is used for arrangements development of governing flow problem. Optimal homotopic solution expressions for velocities and temperature are studied through plots by considering various estimations of physical variables. Moreover the surface drag coefficients and heat transfer rate are analyzed through plots.     

Analysis of triple metal surrounding gate (TM-SG) III–V nanowire MOSFET for photosensing application

In this paper, a low power highly sensitive Triple Metal Surrounding Gate (TM-SG) Nanowire MOSFET photosensor is proposed which uses triple metal gates for controlling short channel effects and III–V compound as the channel material for effective photonic absorption. Most of the conventional FET based photosensors that are available use threshold voltage as the parameter for sensitivity comparison but in this proposed sensor on being exposed to light there is a substantial increase in conductance of the GaAs channel underneath and, thereby change in the subthreshold current under exposure is used as a sensitivity parameter (i.e., I_illumination/I_Dark). In order to further enhance the device performance it is coated with a shell of Al_xGa_1-xAs which effectively passivates the GaAs surface and provides a better carrier confinement at the interface results in an increased photoabsorption. At last performance parameters of TM-SG Bare GaAs Nanowire MOSFET are compared with TM-SG core-shell GaAs/AlGaAs Nanowire MOSFET and the results show that Core-Shell structures can be a better choice for photodetection in visible region.     

Study on the Cofluorescence Effect of Europium (III)–Yttrium (III)–Balofloxacin–Sodium Dodecyl Sulfate System and Its Analytical Application

A new fluorescence enhancement phenomenon in the europium(III)–balofloxacin–sodium dodecyl sulfate system was observed when yttrium(III) was added. Based on this, a sensitive cofluorescence assay for the estimation of balofloxacin was established. Under the optimized conditions, the enhanced fluorescence signal was linear over the concentration of balofloxacin ranging from 3.0 × 10^?9 to 7.0 × 10^?6 mol L^?1 with a correlation coefficient of 0.9993. The detection limit (3 σ) was determined as 8.3 × 10^?10 mol L^?1. The presented method was successfully applied to determination of balofloxacin in pharmaceutical preparations, human serum, and urine. The possible fluorescence enhancement mechanism was also discussed.     

EPR Studies of DOPA–Melanin Complexes with Fe(III)

Paramagnetic centers in 3,4-dihydroxyphenylalanine–melanin and its complexes with Fe(III) were examined by electron paramagnetic resonance (EPR) spectroscopy. Paramagnetic centers of melanin play an important role in detoxification of environment and they reveal high activity in binding of metal ions. Two different signals were observed in EPR spectra: lines of o-semiquinone free radicals and lines of paramagnetic Fe(III). Amplitudes of EPR lines of both free radicals and iron ions decrease with increasing Fe(III) content in melanin–metal ion complexes. Free radical concentrations in the melanin samples, g-factors, amplitudes and line widths of EPR spectra were determined. It was stated that fast spin–lattice relaxation processes exist in both free radical system and paramagnetic iron ions in melanin complexes.     

Spectroscopic and Theoretical Study of Cyanidin–Aluminum (III) Complexes

Complexation of aluminum (III) with cyanidin, a natural anthocyanidin molecule, has been investigated in methanol and buffered solutions of pH 3.0 and 4.0. Electronic absorption spectroscopy was performed to characterize the stoichiometry and stability of the complexes formed. In investigated solvents, aluminum bonded moderately to cyanidin requiring large mole ratios of the components (up to 200) for the access of complexation. Molar ratio plots showed the formation of only one complex with stoichiometry aluminum (III):cyanidin of 1∶1 in both investigated media. Semiempirical calculations, performed in the Austin Model 1 parameterization, enabled the determination of the structural features of free compounds as well as complex structural modifications caused by chelation of Al(III).     

Decoration of multi-walled carbon nanotubes with noble- and transition-metal clusters and formation of CNT–CNT networks

Carbon nanotubes are of great interest because of their outstanding mechanical, chemical and electric properties. The decoration of multi-walled carbon nanotubes with metal clusters of gold, palladium, iron, cobalt and nickel opens even more applications, especially the growth of complex conductor networks in microelectronic devices. PACS 81.07.De; 81.16.Be; 82.30.Nr; 82.33.Hk     

Preparation and performance of sulfur–carbon composite based on hollow carbon nanofiber for lithium-sulfur batteries

A unique structured hollow carbon nanofiber–sulfur composite material (HCF–S) was fabricated and characterized in lithium-sulfur batteries. It is found that a part of spherical sulfur particles are located in the voids formed by the intertwined fibers and the others are confined in hollow channel of the HCF. The high conductive and porous HCF favors the construction of stable three-dimensional conducting network and convenient infiltration of the electrolytes into the cathode. The HCF–S cathode exhibits excellent electrochemical performance in the electrolyte with LiNO₃. By contrast, the ionic liquid electrolyte provides insufficient shuttle suppression and weakens ion transport, which leads to poor cycle and rate capability.     

Strong lithium-polysulfide anchoring effect of amorphous carbon for lithium–sulfur batteries

Solving the shuttle effect caused by lithium polysulfide (LPS) dissolution is important in lithium−sulfur batteries. The anchoring of LPSs to carbon combined with sulfur is a method of suppressing the shuttle effect. This first-principles study is the first to report that amorphous carbon offers the best ability to anchor LPSs. The adsorption energies of LPSs on amorphous carbon are at least six times higher than those on graphene and at least two times higher than those on pyridinic-N doped graphene. The LPSs adsorbed on amorphous carbon undergo significant molecular distortion and/or partial dissociation due to the S-to-C electron transfer of 1.2–1.8 e per molecule, as well as the formation of strong bonds between both the Li and S atoms and the sp- and sp²-site C atoms. We propose an amorphous carbon−graphite hybrid anchoring material, because amorphous carbon can strongly capture LPSs and graphite can act as an electron channel.     

Laser-induced synthesis of metal–carbon materials for implementing surface-enhanced Raman scattering

Metal–carbon materials exhibiting surface-enhanced Raman scattering have been synthesized by laser irradiation of colloidal systems consisting of carbon and noble metal nanoparticles. The dependence of the Raman scattering intensity on the material composition and laser irradiation conditions has been investigated. The possibility of recording the Raman spectrum of organic dye rhodamine 6G, deposited in amount of 10^–6 M on the substrate obtained from a colloidal solution is demonstrated.     

Validation of a lattice Boltzmann model for gas–solid reactions with experiments

A lattice Boltzmann method is used to model gas–solid reactions where the composition of both the gas and solid phase changes with time, while the boundary between phases remains fixed. The flow of the bulk gas phase is treated using a multiple relaxation time MRT D3Q19 model; the dilute reactant is treated as a passive scalar using a single relaxation time BGK D3Q7 model with distinct inter- and intraparticle diffusivities. A first-order reaction is incorporated by modifying the method of Sullivan et al. [13] to include the conversion of a solid reactant. The detailed computational model is able to capture the multiscale physics encountered in reactor systems. Specifically, the model reproduced steady state analytical solutions for the reaction of a porous catalyst sphere (pore scale) and empirical solutions for mass transfer to the surface of a sphere at Re = 10 (particle scale). Excellent quantitative agreement between the model and experiments for the transient reduction of a single, porous sphere of Fe₂O₃ to Fe₃O₄ in CO at 1023 K and 10⁵ Pa is demonstrated. Model solutions for the reduction of a packed bed of Fe₂O₃ (reactor scale) at identical conditions approached those of experiments after 25 s, but required prohibitively long processor times. The presented lattice Boltzmann model resolved successfully mass transport at the pore, particle and reactor scales and highlights the relevance of LB methods for modelling convection, diffusion and reaction physics.     

Surface and interfacial morphologies of PAN-CVI carbon–carbon composite

Scanning electron microscopy (SEM), polarized light microscopy (PLM), and transmission electron microscopy (TEM) techniques have been used to characterize the normal surface and flank surface microstructure of a polyacrylonitrile (PAN)-based carbon fiber reinforced chemical vapor infiltrated (CVI) matrix carbon–carbon composite. Optical and SEM results indicate that the CVI deposit consists of two structures: an isotropic phase is present in the fiber bundle-bundle junctions and a second highly oriented lamellar structure is present in the intrabundle matrix. TEM shows that matrix platelets are highly parallel to the fiber axis and the crystallites of the matrix near the fiber surface exhibit better alignment than those farther away from fibers.     

A highly luminescent complexes of Eu(III) and Tb(III) with norfloxacin and gatifloxacin doped in sol–gel matrix: A comparable approach of using silica doped Tb(III) and Eu(III) as optical sensor

Highly luminescent complexes of Eu and Tb ions with norfloxacin (NFLX) and gatifloxacin (GFLX) were prepared in sol–gel matrix. The red and green emissions of Eu and Tb ions were obtained by the energy transfer from the triplet state of (NFLX) and (GFLX) to the excited emitting states (⁵D₀ and ⁵D₄) of Eu and Tb, respectively. The intensity of the electric field emission bands (⁵D₀→⁷F₂, 617 nm and ⁵D₄→⁷F₅, 545 nm) of Eu and Tb ions were proportional to the concentration of (NFLX at pH 6.0) and (GFLX at pH 3.5) in acetonitrile with excitation wavelengths (λ_ex) (340 and 395) and (370 and 350 nm) for Eu and Tb ions, respectively. The monitored luminescence intensity of the system showed a good linear relationship with the concentration of NFLX within a range of 5×10^?9–5.8×10^?6 and 5×10^?8–1.0×10^?6 mol L^?1 with a correlation coefficient of 0.990, and for GFLX within a range of 2.4×10^?9–3.2×10^?5 and 5×10^?8–8.0×10^?6 mol L^?1 with a correlation coefficient of 0.995. The detection limit (LOD) was determined as 3.0×10^?9 and 1.0×10^?8 mol L^?1 for NFLX and 1.6×10^?10 and 2.0×10^?8mol L^?1 for GFLX. The limit of quantification (LOQ) is 9×10^?9 and 3.0×10^?8 and 4.8×10^?10 and 6.0×10^?8 in case of Eu and Tb, respectively.     

Static versus energy-dependent nucleus–nucleus potential for description of sub-barrier fusion dynamics of _8~(16)O+_(50)~(112,116,120)Sn reactions

The static and energy-dependent nucleus–nucleus potentials are simultaneously used along with the Wong formula for exploration of fusion dynamics of168O+112,116,12050 Sn reactions. The role of internal structure degrees of freedom of colliding pairs, such as inelastic surface vibrations, are examined within the context of coupled channel calculations performed using the code CCFULL. Theoretical calculations based on the static Woods–Saxon potential along with the one-dimensional Wong formula fail to address the fusion data of168O+112,116,12050 Sn reactions.Such discrepancies can be removed if one uses couplings to internal structure degrees of freedom of colliding nuclei.However, the energy-dependent Woods–Saxon potential model(EDWSP model) accurately describes the sub-barrier fusion enhancement of168O+112,116,12050 Sn reactions. Therefore, in sub-barrier fusion dynamics, energy dependence in the nucleus–nucleus potential governs barrier modification effects in a closely similar way to that of the coupled channel approach.