Thermoelectric effects in organic conductors in a strong magnetic field

The linear response of the electron system of a layered conductor to the temperature gradient in this system in a strong magnetic field is investigated theoretically. Thermoelectric emf is studied as a function of the magnitude and orientation of a strong external magnetic field; the experimental investigation of this function, combined with the study of the electric and thermal resistance, allows one to completely determine the structure of the energy spectrum of charge carriers.     

Phosphonobetaine/sulfur dioxide copolymer by Butler’s cyclopolymerization process

The zwitterionic monomer, ethyl 3-(N,N-diallylammonio)propanephosphonate and sulfur dioxide were cyclocopolymerized in DMSO using azobisisobutyronitrile or ammonium persulfate as initiators to afford a pH-responsive polyphosphonobetaine/SO₂ (PPB/SO₂) copolymer. The polymers, on treatment with HCl and NaOH, gave the aqueous solutions of the corresponding cationic polyphosphononic acid (CPP) and anionic polyphosphonate (APP). The solution properties of the PPB having two pH-responsive functionalities were investigated in detail by potentiometric and viscometric techniques. Basicity constants of the amine and phosphonate groups in APP were found to be “apparent” and as such follow the modified Henderson–Hasselbalch equation. The incorporation of SO₂ moiety has resulted in the decrease of basicity constant of the nitrogens in the copolymer by staggering ?2 units of log K in compare to that of the corresponding homopolymer. The basicity difference is expected to have an effect on the chelating properties of the polymers. In contrast to many polycarbo- and -sulfobetaines, the PPB was all found to be soluble in salt-free water as well as in salt (including Ca²⁺ and Li⁺)-added solutions. The PPB demonstrated ‘antipolyelectrolyte’ viscosity behavior and found to have higher viscosity values in LiCl than in NaCl or NaI.     

Spectrophotometric and spectrofluorimetric investigation of different equilibria of a recently synthesized Schiff base with the aid of chemometric methods

In this study ground and excited states acidic dissociation constants of a recently synthesized Schiff base was obtained in a DMF:water mixture of 30:70 (v/v) using absorption and fluorescent spectra of the Schiff base in different pH values with the aid of chemometric methods. In addition, the fluorescent of the two kinds of tautomers of this Schiff base was investigated and the rate of tautomerization was obtained using rank annihilation factor analysis (RAFA). The effect of different kinds of surfactants such as sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB) and Triton X-100 on fluorescence spectrum of the Schiff base in a DMF:water mixture of 2:98 (v/v) was investigated. CTAB increased the fluorescence intensity of the Schiff base while SDS and Triton X-100 had no significant effect on it. β-Cyclodextrin increased the fluorescence intensity of the Schiff base. Also the sensing behavior of this Schiff base toward metal ions was studied in DMF and ethanol by fluorescence spectroscopy. The Schiff base showed prominent fluorescent signal in the presence of Zn²⁺, whereas other metal ions failed to induce response and ground-state dissociation constant of the complex was determined by direct fluorimetric titration as a function of Zn²⁺ concentration.     

Bis­(acesulfamato)­tetra­aqua­cobalt(II)

The crystal structure of the first acesulfame–metal complex, namely tetra­aqua­bis­[6‐methyl‐1,2,3‐oxa­thia­zin‐4(3H)‐onato 2,2‐dioxide‐κN]­cobalt(II), [Co(C₄H₄NO₄S)₂(H₂O)₄], is re­ported. The Co^II ion resides on a twofold axis and is coordinated by four aqua ligands defining the basal plane and by two monodentate acesulfamate ligands, via their ring N atoms, in the axial positions. Two intra‐ and three intermolecular hydrogen‐bonding interactions stabilize the crystal structure and form an infinite three‐dimensional lattice.     

The combinatorial factor method for investigation of surface adsorption

In this work, we have used the combinatorial factor method to find the thermodynamic properties of the monolayer surface adsorption with a limited number of rows and nearest neighbor interactions so that the maximum coordination number of each adsorbed particle could be varied from zero to four. The results show that the thermodynamic properties of models with different number of rows are close to each other. In addition, for adsorbed particles with the nearest neighbor interactions, when the fractional coverage becomes 1/2, a phase transition takes place.     

Oblique interaction of electrostatic nonlinear structures in relativistically degenerate dense magnetoplasmas

We have investigated the interaction of obliquely propagating ion acoustic solitary waves in a magnetoplasma with relativistically degenerate electrons. Using the quantum hydrodynamics model and by employing the extended Poincaré–Lighthill–Kuo technique, we have derived a set of Korteweg de Vries equations for two solitons. We have observed that the system under consideration allows the formation of only compressive solitons and their velocities remain in the sub-acoustic limit. Furthermore, phase shifts of solitons as a result of their interaction have been calculated. The phase shifts have been observed to be dependent on the obliqueness and the physical parameters of plasma. It has also been noticed that phase shifts remain negative for the whole range of parameters generally found in white dwarf stars. We have observed that the phase shifts enhance with the enhancement in number density, however, the converse happens when the magnetic field is enhanced. It has also been observed that the phase shift is slightly greater for the solitons that are less oblique as compared to their more oblique counterparts. Furthermore, we have estimated the spatial scales of interaction of solitons using the parameters found in white dwarf stars.     

Deposition of silica thin films formed by sol–gel method

Deposition of silica thin films on silicon wafer was investigated by in situ mass measurements with a microbalance configured for dip coating. Mass change was recorded with respect to deposition time when the substrate was fully immersed in the silica sol. Mass gain during deposition was higher than predicted from monolayer coverage of silica nano particles. This implied that deposition was facilitated by gelling of the nanoparticles on the substrate. The rate of deposition was enhanced by increasing the particle concentration in the sol and by decreasing the particle size from 12 to 5 nm. Increasing the salt concentration of the silica sol at constant pH enhanced the deposition of the silica particles. Reducing the pH of the sol from 10 to 6 decreased the deposition rate due to aggregation of the primary silica particles.     

Photoredox reactions of Cr(III) mixed-ligand complexes

Irradiation of chromium(III) complexes with oxalate and pyridinedicarboxylate ligands (pda = 2,3-, 2,4-, or 2,5-dicarboxylate) leads to diverse behaviors, dictated by light energy, presence of oxygen and the ligand nature. Irradiation within the MC bands is unaffected by O₂ and results in ligand substitution. The LMCT excitation is effective only when oxalate is coordinated to Cr(III); then electron transfer from oxalate to central ion generates an intermediate, consisted of a Cr(II)species and the C₂O₄^? radicals. The species undergo fast redox reactions dependent on the presence of O₂ and the pda ligand.(1) In anoxic medium the fast outersphere electron transfer from Cr(II) to solvent, generates hydrated electrons and re-oxidizes the chromium centre to Cr^III. Then geminate recombination regenerates substrate, whereas competitive release of the C₂O₄^? radical leads to substitution of one oxalate ligand by two water molecules (aquation induced by the LMCT excitation). In the presence of the pda ligand the outersphere electron transfer is accompanied by the innersphere CT, generating Cr(III) coordinated to two radical ligands: C₂O₄^? and pda^3?; the intermediate releases also e_aq^?, but this reaction is slower than that of the homoleptic oxalate complex. Hydrated electrons are scavenged also by the released radicals. All these processes are completed within microseconds and in consequence, the Cr(III) complexes irradiated in deoxygenated solutions are insensitive to subsequent oxygenation.(2) When UV-irradiation is carried out in oxygenated medium reaction of Cr(II) species with molecular oxygen competes with the outer- or inner electron transfer observed in anoxic medium. Both these pathways result in generation of chromate(VI). Quantum yield of the Cr(VI) production is sensitive to the presence and structure of pda ligand, decreasing within the series 2,3-pda > 2,4-pda > 2,5-pda.     

Synthesis of 3,5-diaryl-4-chlorophthalates by [4+2] cycloaddition of 1-ethoxy-2-chloro-1,3-bis(trimethylsilyloxy)-1,3-diene with dimethyl acetylenedicarboxylate and subsequent site-selective Suzuki-Miyaura reactions

The [4+2] cycloaddition of 1-ethoxy-2-chloro-1,3-bis(trimethylsilyloxy)-1,3-diene with dimethyl acetylenedicarboxylate (DMAD) afforded dimethyl 4-chloro-3,5-dihydroxyphthalate. Site-selective Suzuki-Miyaura reactions of its bis(triflate) provide a convenient approach to 3,5-diaryl-4-chlorophthalates containing two different aryl groups.