XPS study of the oxidation of nanosize Ni/Si(100) films

The XPS (X-ray photoelectron spectroscopy) study of nickel oxide nanolayers obtained by magnetron sputtering of the metal and its subsequent oxidation in air at different temperatures (400°C and 1000°C) was performed. Silicon(100) was used as a substrate. Surface of the initial Ni/Si structure was shown to contain not only Ni metal, but also the NiO oxide. Annealing at 400°C results in a complete oxidation of the metal film. At a high-temperature annealing (1000°C), nickel interacts both with oxygen and silicon substrate to form NiSi silicide and a composite Ni-Si-O phase in transition layer. Electronconductivity of NiO films is determined by intercrystallite barriers. Activation energies of film electroconductivity in model gases (O₂, Ar, H₂) were found.     

Conductivity of low-temperature KF-AlF<Subscript>3</Subscript> electrolytes containing lithium fluoride and alumina

Electroconductance of molten electrolytes KF-AlF₃ (cryolite ratio 1.3) containing LiF or/and Al₂O₃ is evaluated using empirical equations. The electroconductivity of molten mixtures KF-AlF₃, KF-AlF₃-Al₂O₃, KF-AlF₃-LiF, and KF-AlF₃-LiF-Al₂O₃ is measured in the temperature interval 687 to 797°C. The electroconductivity is determined in cells with a capillary of pyrolytic boron nitride and parallel molybdenum electrodes. Comparing calculated and experimental data on the electroconductivity of cryolite-alumina melts confirms that the model proposed for the calculations reflects the temperature and concentration dependences adequately enough and makes it possible to forecast variations in the electroconductivity upon adding different admixtures into the electrolyte.     

The Synthesis of Porous Na3V2(PO4)3 for Sodium-Ion Storage

Na₃V₂(PO₄)₃ (NVP) has been regarded as a potential cathode material for sodium-ion batteries (SIBs) due to its excellent structural stability and rapid Na⁺ conductivity. However, its electrochemical performances are restricted by the large bulk structure and poor electronic conductivity. The construction of porous NVP materials is a powerful method to improve the electrochemical properties. This concept aims to provide an overview of recent progress of porous NVP materials for SIBs. Herein, the synthetic strategies and formation mechanisms of porous NVP materials as well as the relationship between the porous structures and electrochemical performances of NVP materials are reviewed. Furthermore, the challenges and prospects for the preparation of porous NVP materials in this field are outlined.     

Bulk Modification of Carbon Paste Electrode with Bi2O3 Nanoparticles and Its Application as an Electrochemical Sensor for Selective Sensing of AntiHIV Drug Nevirapine

Bi₂O₃ nanoparticles were synthesized by solution combustion method and utilized for fabrication of an electrochemical sensor [carbon paste electrode modified with Bi₂O₃ (CPE‐Bi₂O₃)] for nevirapine (NVP). Electrode materials were characterized by XRD, FTIR, TG‐DTA, AFM and SEM‐EDS methods. CPE‐Bi₂O₃ was electroreduced (Er) in KOH in the potential range of ?1.3–0 V to obtain CPE‐ErBi₂O₃. CPE‐ErBi₂O₃ exhibited electrocatalytic activity towards the oxidation of NVP. Under optimized conditions, linearity between the peak current and NVP concentration was observed in the range of 0.05–50 µM. Further, the sensor was used for the assay of NVP in tablets and biological samples.     

B2N2-Embedded Polycyclic Aromatic Hydrocarbons with Furan and Thiophene Derivatives Functionalized in Crossed Directions

A series of polycyclic aromatic hydrocarbons (PAHs), consisting of two pairs of BN units, have been designed and their synthesis has been achieved by electrophilic C−H borylation. Two conjugation extension directions can be found in these B₂N₂-embedded PAHs. The B₂N₂-containing backbone with shorter effective conjugation length is isoelectronic with diaryl-fused anthracene, whereas the second derivative, with longer effective conjugation length, is isoelectronic with bis(trans-arylvinyl)benzene. By incorporating different aryl groups, i.e., furyl, thienyl, benzo[b]furyl, and benzo[b]thienyl groups, into the two crossed directions of the B₂N₂-embedded PAHs, their electronic and optical properties have been comparatively investigated by photophysical, electrochemical, and theoretical approaches. It is found that both the substituents and their conjugation extension directions have significant effects on the aromatic and photophysical properties of the B₂N₂-embedded PAHs. The conjugation extension in the shorter backbone is more pronounced on the effective conjugation length than the longer backbone. Moreover, all the B₂N₂-embedded PAHs behave as both Lewis acids and Lewis bases, and reversible photoluminescence switching can be observed by simply neutralizing the added Lewis acid or Lewis base.     

Electrophysical characteristics and stability of solid apatite-like electrolytes La x Si6O12 + 1.5x and La x Ge6O12 + 1.5x

Oxygen-ion conduction in apatite-like compounds based on silicates and germanates of lanthanum La _x A₆O_{12 + 1.5x} (A = Si, Ge; x = 9.11–10.22) is studied. The compounds are shown to be purely ionic conductors at 600–900°C and partial oxygen pressures 10^?16 to 10⁵ Pa. The electroconductivity of the best conducting specimens of La _x A₆O_{12 + 1.5x} (A = Si, Ge; x = 9.77–10) exceeds that of electrolyte YSZ at moderate temperatures. The electroconductivity of lanthanum germanate is substantially greater than that of lanthanum silicate, specifically, 7.85 × 10^?2 and 2.35 × 10^?2 S cm^?1, respectively, at 800°C. An inflection is discovered at ～750°C in the temperature dependences of electroconductivity of La _x Ge₆O_{12 + 1.5x} (x = 9.77–10.22). A dilatometric examination points to a second-kind phase transition that may be due to the oxygen sublattice disordering. The behavior of apatite-like electrolytes La _x A₆O_{12 + 1.5x} (A = Si, Ge) during long exploitation periods in the interval of working temperatures of electrochemical devices is studied for the first time ever. The electrolytes’ aging at 800°C in air for 1000 h was investigated by the electroconductivity method. The electroconductivity of lanthanum germanates decayed with time by 5% and that of lanthanum silicates, by 9.5%. The steady-state values of electroconductivity of all compounds studied is reached after 600–700 h. The compounds studied form a class of materials that hold some promise as solid electrolytes for medium-temperature fuel cells and other electrochemical devices.     

A Superior Na3V2(PO4)3‐Based Nanocomposite Enhanced by Both N‐Doped Coating Carbon and Graphene as the Cathode for Sodium‐Ion Batteries

A superior Na₃V₂(PO₄)₃‐based nanocomposite (NVP/C/rGO) has been successfully developed by a facile carbothermal reduction method using one most‐common chelator, disodium ethylenediamintetraacetate [Na₂(C₁₀H₁₆N₂O₈)], as both sodium and nitrogen‐doped carbon sources for the first time. 2D‐reduced graphene oxide (rGO) nanosheets are also employed as highly conductive additives to facilitate the electrical conductivity and limit the growth of NVP nanoparticles. When used as the cathode material for sodium‐ion batteries, the NVP/C/rGO nanocomposite exhibits the highest discharge capacity, the best high‐rate capabilities and prolonged cycling life compared to the pristine NVP and single‐carbon‐modified NVP/C. Specifically, the 0.1 C discharge capacity delivered by the NVP/C/rGO is 116.8 mAh g^?1, which is obviously higher than 106 and 112.3 mAh g^?1 for the NVP/C and pristine NVP respectively; it can still deliver a specific capacity of about 80 mAh g^?1 even at a high rate up to 30 C; and its capacity decay is as low as 0.0355 % per cycle when cycled at 0.2 C. Furthermore, the electrochemical impedance spectroscopy was also implemented to compare the electrode kinetics of all three NVP‐based cathodes including the apparent Na diffusion coefficients and charge‐transfer resistances.     

The influence of oxidation number of sulfur on the polymerization and thermo-mechanical properties of dimethacrylate copolymers

Structure and characterization of the sulfur-containing monomers bis[4(2-hydroxy-3-methacryloyloxypropoxy)phenyl]sulfide (S·DM), bis[4(2-hydroxy-3-methacryloyloxypropoxy)phenyl]sulfinyl (SO·DM), bis[4(2-hydroxy-3-methacryloyloxypropoxy)phenyl]sulfonyl (SO₂·DM), and their photopolymerization with N-vinyl-2-pyrrolidone (NVP) are presented. The monomers were obtained in the reaction of derivatives of aromatic diols with 2-(chloromethyl)oxirane in the two-phase liquid/liquid system, including organic and aqueous phases. Next, esterification of the obtained diglycidyl ether was carried out with the use of methacrylic acid. Photopolymerization of the compositions (S·DM, SO·DM, SO₂·DM and NVP) and the initiator (Irgacure 651) was carried out. The influence of oxidation number of sulfur on the properties of the obtained copolymers was studied. The following properties were determined: density, glass transition temperature, Young’s modulus, hardness and tensile strength. Additionally, dynamic-mechanical and thermal properties were investigated. Thermal properties of copolymers under different conditions (in air, in nitrogen and in helium) were tested.     

Electroconductivity of Lithium Perchlorate Solutions in Sulfolane Mixtures with 1,2-Dimethoxyethane

The electroconductivity, viscosity, and density of 1 M LiClO₄solutions in sulfolane mixed with 1,2-dimethoxyethane are measured. Some of the measured quantities deviate from additivity. A maximum of LiClO₄electroconductivity in the mixture occurs at a 1 : 2 molar ratio of sulfolane to dimethoxyethane. The electroconductivity increase is presumably due to improved transport properties of the system.     

COads spillover and low-temperature activity of heterophase catalysts in CO oxidation

The kinetics of CO oxidation on heterophase surfaces composed of two different types of patches M1 and M2 is analyzed. The kinetic conjugation of the patches caused by CO_ads spillover leads to the substantial change in reaction rate temperature dependences, as well as to the appearance of a low-temperature, superadditive activity.     

Synthesis and properties of a series of well-defined and polydisperse benzo[1,2-b:4,3-b']dithiophene oligomers

Monodisperse and polydisperse oligomers of benzo[1,2-b:4,3-b']dithiophene (BDT) (1-14), including three types of oligomers with different spacers combining BDT units (direct linkage, vinylene spacers, and ethynylene spacers), were synthesized, and their thermal, optical, and electrochemical properties were investigated. The oligomers were synthesized using Suzuki, Stille, Wittig, and Sonogashira coupling reactions. All of the monodisperse oligomers showed high melting points and 5% weight loss temperatures (T(d) > 400 degrees C). The fluorescence maxima of all oligomers were red-shifted, and the emission colors varied from blue to yellow as the chain lengths-and thus the conjugation lengths-increased. The vinylene-bridged oligomers emitted at longer wavelengths than the direct-linked and ethynylene-bridged oligomers. UV-vis absorption spectra in toluene solution indicated an effective conjugation length of about six BDT units for polydisperse oligomer 5. Cyclic voltammetry measurement indicated that tetramer 3 had high electrochemical stability. Although tetramer 3 and vinylene-bridged tetramer 8 exhibited reversible oxidation waves, ethynylene-bridged tetramer 13 showed an irreversible oxidation process. Each type of monodisperse oligomer exhibited higher HOMO levels with increasing chain length.     

Solvation Interactions in Solutions of Lithium Hexafluoroarsenate in Propylene Carbonate

On the basis of the dissolution heat in propylene carbonate (PC) measured at 298.15 K, and the electroconductivity, ultrasound propagation velocity, and solution density and viscosity measured at 283.15–313.15 K, the LiAsF₆ solvation in PC is discussed. The LiAsF₆ solvation enthalpy and its ionic components are determined. It is shown that the donor–acceptor interaction between Li⁺ and the oxygen atom of the carbonyl group of PC makes the main contribution to the enthalpy. The effects of the concentration and temperature on the molar electroconductivity, viscosity, apparent molar volume, and electrolyte compressibility are analyzed, and thermodynamic parameters of the activation of viscous flow and electroconductivity are considered. Using the Onori approach, parameters of solvation complexes in solution, such as solvation numbers, volumes, compressibilities, and their dependences on the concentration are determined. A considerable solvent compressibility is noted in the inner sphere of the complex.     

Oxidation of 2-hydroxynevirapine, a phenolic metabolite of the anti-HIV drug nevirapine: evidence for an unusual pyridine ring contraction

Nevirapine (NVP) is an anti-HIV drug associated with severe hepatotoxicity and skin rashes, which raises concerns about its chronic administration. There is increasing evidence that metabolic activation to reactive electrophiles capable of reacting with bionucleophiles is likely to be involved in the initiation of these toxic responses. Phase I NVP metabolism involves oxidation of the 4-methyl substituent and the formation of phenolic derivatives that are conceivably capable of undergoing further metabolic oxidation to electrophilic quinoid species prone to react with bionucleophiles. The covalent adducts thus formed might be at the genesis of toxic responses. As part of a program aimed at evaluating the possible contribution of quinoid derivatives of Phase I phenolic NVP metabolites to the toxic responses elicited by the parent drug, we have investigated the oxidation of 2-hydroxy-NVP with dipotassium nitroso-disulfonate (Frémy's salt), mimicking the one-electron oxidation involved in enzyme-mediated metabolic oxidations. We report herein the isolation and full structural characterization of a 1H-pyrrole-2,5-dione derivative as a major product, stemming from an unusual pyridine ring contraction.     

Synthesis and properties of π‐conjugated dithiafulvene oligomers by addition of a monofunctionalized compound

Dithiafulvene oligomers ( 3 ) were prepared by cycloaddition polymerization of aldothioketenes with their alkynethiol tautomers derived from 1,4‐diethynylbenzene ( 2 ) with the addition of 1‐ethynyl‐4‐methylbenzene ( 1 ) as a monofunctionalized compound. Different feed ratios of 2 / 1 were used to control the molecular weights of 3 . The structures of 3 were confirmed by IR and ¹H NMR spectroscopies in comparison with those of 2‐(4‐tolylidene)‐4‐tolyl‐1,3‐dithiol ( 4 ) as a model compound, which was obtained by the treatment of lithium 2‐tolylethynethiolate with water in Et₂O. The number‐average degree of polymerization (DP) and the number‐average molecular weight were measured by gel permeation chromatographic and ¹H NMR analysis. DP increased with an increasing feed ratio of 2 / 1 . The ultraviolet–visible spectra of 3 in diluted acetonitrile showed that the absorption maxima of 3 increased with an increasing DP of 3 . These redshifts are ascribed to an effective expansion of the π‐conjugation system in 3 . The oligomers exhibited a maximum conjugation length of seven repeating units. The redox properties of 3 were examined by cyclic voltammetry. The oxidation half‐peak potentials (E_p/2) of 3 were slightly cathodically shifted with increasing DP. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 708–715, 2003     

Synthesis and characterization of novel polymer-drug conjugate based on the anhydride containing copolymer as a potential method for drug carrier

5-Fluorouracil (5FU) is in clinical use as an antitumor agent for the treatment of several types of solid tumors and cancers. However, development of drug resistance within the tumor cells and side effects has been a major limitation for the clinical use of 5FU. Preparation polymer-5FU conjugation is a promising potential antitumor drug and alternative pathway that could be used to treatment of cancer. For this purpose, water soluble poly(maleic anhydride-alt-N-vinyl pyrrolidone)[Poly(MA-alt-NVP)] is synthesized via charge transfer complex (CTC) copolymerization with benzoyl peroxide as an initiator at 80°C under nitrogen atmosphere. CTC mechanism is formed between through MA and NVP by determined using Uv-vis spectroscopy. Molar absorption coefficient (?^AD) and equilibrium constant (K^AD) of the complex are determined by Scott equation. The results obtained from indicate that copolymerization of MA:NVP system is preceded via alternating mechanism. The compositions of synthesized copolymers are also investigated by elemental analysis and the reactivity ratios of these monomers are calculated by using the elemental analysis data through Kelen-Tüdös, Mayo-Lewis, Fineman-Ross and Inverted Fineman-Ross equations. For preparation of polymer-drug conjugate, chemical modification is employed between the copolymer and 5FU. Polymer-drug conjugate and conjugation mechanism are enlightened by ATR-FTIR, NMR, HR-Raman and XRD methods.     

Collapsed conformation of poly(methacrylic acid) chain containing nonionic hydrophilic units

Copolymers of methacrylic acid (MAA) and a nonionic hydrophilic monomer N-vinylpyrrolidone (NVP) were synthesized by polymerization in aqueous solution in the absence of metal ions. The NVP content of the copolymers ranged from 2 to 36 mole % with sequences of MAA interrupted at random by a single unit of NVP at all compositions. The pH-induced conformational transition of these copolymers was followed by potentiometric titration and viscosity studies and the results were compared with those of pure poly(methacrylic acid) (PMAA). The negative free energy of transition from the un-ionized compact from to expanded structure showed a gradual decrease with increasing NVP content, and the collapsed conformation observable for PMAA at low degrees of ionization (0 < α < 0.3) disappeared at NVP contents greater than 15 mole%. These findings are supported by viscosity data. The results suggest that long-range methyl–methyl hydrophobic contacts still possible in higher NVP content copolymers are not sufficient to bring about the collapse of the molecule and a minimum average sequence length of about 20 MAA units is required to compact the molecule. Hydrophilic “shielding” of MAA chains by NVP segments could also partly destabilize the collapsed structure.     

Synthesis of copolymers of N-vinylpyrrolidone and 2-ethylhexyl acrylate by DL-methionine-mediated reversible deactivation radical polymerization and their dispersion behavior in preparation of LiFePO4 battery positive slurry with high solid content

Dispersants play a significant role in the formulation of positive battery slurry. Adding a small amount of dispersant can effectively reduce the viscosity of the slurry, which is beneficial for the production of positive batteries. A series of copolymers of N-vinylpyrrolidone (NVP) and 2-ethylhexyl acrylate (2-EHA) with different molar ratios of NVP to 2-EHA, different polymer molecular weights and different polymer structures are synthesized by dl -methionine-mediated reversible deactivation radical polymerization. The ability of these copolymers to disperse LiFePO₄ battery positive slurry with a high solid content (57.08%) as dispersants has been evaluated. Research shows that when the ratio of NVP to 2-EHA is 20 and the polymer molecular weight is 6000, poly(N-vinylpyrrolidone-ran-2-ethylhexyl acrylate) (NVP-ran-2-EHA) exhibits the strongest dispersing ability to the slurry. This polymer can reduce the viscosity of the slurry by 43.925% and has the longest stabilization time of 3 h, which is better than poly(N-vinylpyrrolidone) (PVP) and poly(N-vinylpyrrolidone)-block-poly(2-ethylhexyl acrylate) (PVP-b-PEHA) with the same molecular weight.     

Basicity of carbonyl complexes of transition metals : X . Interaction of (π-C5H5)Mn(CO)(Ph2PCH2CH2PPh2) with aprotic acids in solution

The interaction of CpMn(CO)(Ph₂PCH₂CH₂PPh₂) with some aprotic acids in solution has been studied by infrared, electronic and ESR spectroscopy and electroconductivity. It is shown, that reactions with π-acids and some π-complexes such as CpTiX₃, CP₂MCl₂ (M  Ti, Zr, Hf, V) take place with oxidation of the manganese atom electron transfer to the acceptor molecule and the formation of the cation-radical of the donor molecule. It is also shown that an increase in the oxidation state of the Mn atom occurs in the reactions with halides of Al, Ti, Sn and Hg and the structure of the products is discussed. Less basic complexes CpMn(CO)₃, Et₅C₅Mn(CO)₃ and Et₅C₅Mn(CO)₂PPh₃ are not oxidised in the presence of tetracyanoethylene but form charge-transfer complexes.     

Effect of pH on the reactivity ratios in aqueous solution copolymerization of acrylic acid and N-vinylpyrrolidone

Acrylic acid (AA) and N-vinylpyrrolidone (NVP) were copolymerized in aqueous solution at 30°C in the pH range 4–9 and the monomer reactivity ratios (r₁ for AA and r₂ for NVP) were determined as a function of pH from the high conversion data by using both the differential (YBR) and the integrated copolymerization equations. The value of r₁ decreased from 5.2 at pH 4 to a minimum of 1.3 at pH 5 and then increased to 8.1, 6.6, and 7.2 at pH 7, 8, and 9, respectively. Addition of 1M NaCl at pH 6.5 restored the r₁ nearly to that at pH 4, the predominantly un-ionized acid. The r₂ values for NVP were nearly zero at all pH values except at pH 5. The variation of the reactivity ratios with pH was examined in terms of the electrostatic interactions between the ionized monomer molecules, the rate of homopolymerization of acrylic acid, and the cation binding to the poly(acrylic acid) molecules. The r₂ values for NVP compared favorably with the literature values reported in bulk and organic solvent systems, although r₁ values are much higher.