Esr Study of C60 N- Anion Radicals in DMSO Solution

Abstract

With the aim to stabilize reduced C₆₀ molecules of solid fulleride as free anion radicals in solution, Na_xC₆₀ (x=l, 10) was dissolved in DMSO. The Na_xC₆₀ was chosen among the other alkali-metal fullerides due to the possibility to increase a number of intercalated Na atoms in a fee. lattice of C₆₀ A sufficiently high concentration of C₆₀ anion radicals of an order of magnitude larger than that usually achieved in solution by an electrochemical reduction was obtained. The sharp resonances with the linewidths of order of 0.1 G and with g=2.0004(6) ?2.0012(8) of the room temperature ESR spectra of fluid solution were assigned from mono- to pentaanions of C₆₀. An appearance of additional sharp peaks at g=2.0016–2.0019 in the spectra of solution of nominal Na₁₀C₆₀, but Na₁C₆₀, tentatively related to C₆₀ ^n- with n>6. The results of this study showed a simple approach in an accomplishment of highly concentrated solutions of free anion radicals C₆₀ ^n-, as well as in stabilization of the anion radicals with increased n. In this way a homogeneity of alkali metal intercalation and characteristics of the solvent will be important.     

Solvent influence on isomer separation and conformation control of the cyclohexanedicarboxylate ligand toward La(III) coordination polymeric framework

Two novel coordination polymers have been synthesized using 1,4-cyclohexanedicarboxylic acid (chdcH₂) by the solvent diffusion method. In the presence of different solvents, cis and trans conformations of chdcH₂ were completely separated. The reaction in DMF/glycol resulted in a 1D chain framework La(cis-chdc)(DMF)₂(NO₃) (1) and the reaction in DMSO resulted in the formation of a novel 3D ReO₃ topology La₂(trans-chdc)₃(DMSO)₄ (2). Additionally, the solvent molecules (DMF and DMSO) also acted as coordination ligands in the formation of extended structures.     

Organic superconductors with an incommensurate anion structure

Abstract

Superconducting incommensurate organic composite crystals based on the methylenedithio-tetraselenafulvalene (MDT-TSF) series donors, where the energy band filling deviates from the usual 3/4-filled, are reviewed. The incommensurate anion potential reconstructs the Fermi surface for both (MDT-TSF)(AuI₂)_0.436 and (MDT-ST)(I₃)_0.417 neither by the fundamental anion periodicity q nor by 2q, but by 3q, where MDT-ST is 5H-2-(1,3-dithiol-2-ylidene)-1,3-diselena-4,6-dithiapentalene, and q is the reciprocal lattice vector of the anion lattice. The selection rule of the reconstructing vectors is associated with the magnitude of the incommensurate potential. The considerably large interlayer transfer integral and three-dimensional superconducting properties are due to the direct donor–donor interactions coming from the characteristic corrugated conducting sheet structure. The materials with high superconducting transition temperature, T_c, have large ratios of the observed cyclotron masses to the bare ones, which indicates that the strength of the many-body effect is the major determinant of T_c. (MDT-TS)(AuI₂)_0.441 shows a metal–insulator transition at T_MI=50 K, where MDT-TS is 5H-2-(1,3-diselenol-2-ylidene)-1,3,4,6-tetrathiapentalene, and the insulating phase is an antiferromagnet with a high Néel temperature (T_N=50 K) and a high spin–flop field (B_sf=6.9 T). There is a possibility that this material is an incommensurate Mott insulator. Hydrostatic pressure suppresses the insulating state and induces superconductivity at T_c=3.2 K above 1.05 GPa, where T_c rises to the maximum, T_c^max=4.9 K at 1.27 GPa. This compound shows a usual temperature–pressure phase diagram, in which the superconducting phase borders on the antiferromagnetic insulating phase, despite the unusual band filling.     

Effects of Intense Ultrasound Treatment of C60 Solutions

Abstract

C₆₀ was treated at room temperature, in air with intense ultrasound in the following solvents; decalin, tetralin. cyclohexane and CCl₄. It is shown by UV-VIS and FT-IR spectroscopy that in decalin and in tetralin the dominant reaction seems to be a sono-oxidation, although more complex reactions involving the solvent take place. In CC1₄ sono-oxidation is accompanied by an extensive sono-polymerization. Products in CCl₄ are C₆₀O, C₆₀O₂ and others; the sonopolymer collected from sonicated CCl₄ was easily identified by FT-IR spectroscopy. Sonopolymerization occurs also in decalin and tetralin and is promoted by free radicals as in the case of CCl₄. No reactions are observed in cyclohexane due to the very low solubility of C₆₀ in this solvent and the poor cavitation ability of cyclohexane under the action of ultrasound.     

Photoinduced Electron Transfer to Fulleropyrrolidinium Salts Studied by EPR

The photoinduced formation of fullerene anion radicals from mono- and bis-N-methylfulleropyrrolidinium salts in the presence of TiO₂ or triethylamine as electron donating substrates was investigated using in situ EPR spectroscopy in various solvent mixtures. The photoreduction yield and stability of anion radicals generated are affected by the solvent properties, such as relative permittivity and hydrogen bond donation ability.     

Gelation theory for solutions of polymers with loci of strong interaction

This paper presents a statistical mechanical analysis of gelation in certain solutions ofA/B copolymers. Repeat unitsA, the major units, must constitute about 90 mole% or more of the copolymer, and are compatible with the solvent. Repeat unitsB, the minor units, must be totally incompatible with the solvent and represent loci of strong interaction between the macromolecular chains. If these interactions are sufficiently strong they can lead to gelation of the mixture. The following simplifications of the model afford results that can be expressed in simple, closed form: (1) TheB units are uniformly distributed along the chain backbone. (2) Polymer concentration must be greater then that for chain overlap. (3)B–B interactions lead to dimerization ofB units only. Examples include: (1) Any aqueous polymer solution where theA repeat units are hydrophilic and theB repeat units are hydrophobic;B–B interactions are thus by hydrophobic bonding. (2) Neutralized acrylic acid/acrylamide copolymers where theB are acrylamide repeat units which associate by hydrogen bonds. (3) Ionomer solutions whereB–B bonding is by dipole-dipole interaction. The results show that there is a critical copolymer concentration for gel formation, C _c . It turns out that C _c decreases withB content for low dimerization energies and increases withB content for higher dimerization energies. At intermediate dimerization energies, C _c is insensitive to theB content. The two extreme regimes of behavior are similar to contradictory predictions of previously published theories. Received: 18 September 2000 / Reviewed and accepted: 20 September 2000     

Synthesis and Structure of U(VI), Np(VI), and Pu(VI) 2-Fluorobenzoates

The compounds NH₄[AnO₂(C₆H₄FCOO₃], where An = U (I), Np (II), or Pu (III), CgH₄COO^? is the 2-fluorobenzoate anion, were synthesized and studied by single crystal X-ray diffraction. Compounds I–III are isostructural and crystallize in the cubic system, space group P2₁3, Z = 4. The main structural units of I–III are mononuclear complexes [AnO₂(C₆H₄COO)₃]^? belonging to crystal-chemical group AB₃¹ (A = AnO₂²⁺, B⁰¹ = C₆H₄FCOO^?). The actinide contraction in the structures of I–III is manifested in a regular decrease in the lengths of the An=0 bonds in the AnO₂²⁺ cations and in the volumes of the Voronoi-Dirichlet polyhedra (VDPs) of the An atoms in the series U-Np-Pu. The intermolecular interactions in crystal structures of I–III were analyzed by the method of molecular VDPs.

     

A Spin Resonance Investigation of Magnetism and Dynamics in the Charge-transfer Salts β"-(BEDT-TTF)4[(H3O)M(C2O4)3]S

We report a spin resonance study of the family of quasi-two-dimensional organic (super)conductors β”-(BEDT-TTF)₄[(H₃O)M(C₂O₄)₃]S, where M is a 3d transition metal ion and S is a host solvent molecule. The spin systems for M = Cr³⁺ (S = 3/2) and M = Fe³⁺ (S = 5/2) are investigated by means of both resonant and field modulation techniques in the frequency range between 50 and 313 GHz. The role of the different solvent molecules in determining the degree of spin-orbit coupling and the local symmetry at the metal ion site is established. The low temperature behaviour of intensities, positions and widths of the resonant lines shows significant modifications of the spin-orbit coupling, and of the inter-and intra-ionic spin-spin inter actions. Despite the onset of a weak antiferromagnetic internal field at low temperature, the ultimate narrowing of the lines suggests spin-lattice interactions may still be the dominant relaxation process. Diamagnetic screening in the mixed state of the superconducting samples for fields parallel to the quasi-two-dimensional layers induces additional lineshifts only below B = 2.5T and T = 4K, determining the threshold of full field penetration within the anion layers.     

Kinetics of free radicals in the plasma of a spark discharge in methane

The kinetics of reactions in the plasma of a spark discharge in methane at atmospheric pressure is analyzed using numerical simulation, taking account of the gas-dynamic expansion of the channel. The processes leading to the formation and annihilation of CH _x radicals are investigated and the conditions under which their maximum concentration is reached are determined. The results obtained are of interest for plasma chemical technologies for processing natural gas. Pis’ma Zh. Tekh. Fiz. 25, 82–86 (October 12, 1999)     

Investigation on photogenerated radicals of some carboxylates in solution and in aqueous dispersions of AgBr

Abstract

The photogenerated free radicals from formate, oxalate and acetate in aqueous solutions without and with dispered AgBr grains under illuminations of 355 nm laser light, natural light and monochromatic red, green or blue light were detected by electron spin resonance with spin-trap DMPO. The results showed that: (a) ·CO₂^? radicals were produced in the formate solution by all of these illuminations; (b) the signals of ·CO₂^? radicals were greatly intensified when an AgBr dispersion was present in the formate solution; (c) the signals of ·CO₂^? radicals in the oxalate solution were also detected and intensified when an AgBr dispersion was present, but only after illumination by the 355 nm laser; (d) ·CH₃ radicals, instead of ·CO₂^?, were weakly detected in the acetate solution, but only in the presence of AgBr under illumination by the 355 nm laser. The photochemical behaviour of these carboxylates, particularly formate and oxalate, perhaps implies their capability for trapping photogenerated holes and their potential for acting as a hole converter to an effective electron carrier.     

Photocatalytic degradation of organic pollutants and inactivation of pathogens under visible light via CoOx surface-modified Rh/Sb-doped SrTiO3 nanocube

Visible light-active rhodium and antimony-co-doped SrTiO₃ nanocubes (Rh/Sb:SrTiO₃ NCs) were synthesized at low temperatures from Rh/Sb:TiO₂ nanorods by the molten salt flux method. The effects of different calcination temperatures (700, 800, and 900 °C) and addition of transition metal oxides (NiO_x, CoO_x, and CuO_x) on the photocatalytic properties of the Rh/Sb:SrTiO₃ NCs were studied. The phase composition and morphology of the Rh/Sb:SrTiO₃ NC photocatalysts (after calcination) were characterized using standard analytical techniques. The synergistic effect of the metal oxides and Rh/Sb:SrTiO₃ NCs boosted the photocatalytic degradation of orange II dye and bisphenol A as well as the inactivation of bacteria. 2 wt% CoO_x-loaded Rh/Sb:SrTiO₃ photocatalyst showed higher photocatalytic performance for the degradation of orange II (96.3%) and bisphenol A (87%) in aqueous solution than Ni (2 wt%) and Cu (2 wt%)-loaded Rh/Sb:SrTiO₃ NC composites. In addition, inactivation of Escherichia coli (96%) and Staphylococcus aureus (97.1%) was achieved over CoO_x (2 wt%)-loaded Rh/Sb:SrTiO₃ for 2 h under visible light irradiation (λ?≥?420 nm). Further, scavenging experiments confirmed that superoxide anion radicals (^·O₂^?) and holes (h⁺) are the major active species and OH^· is a minor species responsible for the photocatalytic degradation of the studied organic pollutants. The synthetic strategy presented here offers a novel approach to the design of highly active visible light active photocatalysts for the removal of organic pollutants and inactivation of bacteria in wastewater.

Graphical abstract

     

Development and characterization of clay facial mask containing turmeric extract solid dispersion

Objective: To develop clay facial mask containing turmeric extract solid dispersion (TESD) for enhancing curcumin water solubility and permeability and to determine suitable clay based facial mask.

Methods: The TESD were prepared by solvent and melting solvent method with various TE to polyvinylpyrrolidone (PVP) K30 mass ratios. The physicochemical properties, water solubility, and permeability were examined. The effects of clay types on physical stability of TESD, water adsorption, and curcumin adsorption capacity were evaluated.

Results: The TESD prepared by solvent method with a TE to PVP K30 mass ratio of 1:2 showed physically stable, dry powders, when mixed with clay. When TESD was dissolved in water, the obtained TESD micelles showed spherical shape with mean size of ～100?nm resulting in a substantial enhancement of curcumin water solubility,?～5?mg/ml. Bentonite (Bent) and mica (M) showed the highest water adsorption capacity. The TESD’s color was altered when mixed with Bent, titanium dioxide (TiO₂) and zinc oxide (ZnO) indicating curcumin instability. Talcum (Talc) showed the greatest curcumin adsorption followed by M and kaolin (K), respectively. Consequently, in vitro permeation studies of the TESD mixed with Talc showed lowest curcumin permeation, while TESD mixed with M or K showed similar permeation profile as free TESD solutions. The developed TESD-based clay facial mask showed lower curcumin permeation as compared to those formulations with Tween 80.

Conclusion: The water solubility and permeability of curcumin in clay based facial mask could be improved using solid dispersion technique and suitable clay base composed of K, M, and Talc.     

Enhancement of oral bioavailability of anti-HIV drug rilpivirine HCl through nanosponge formulation*

Objective: To synthesize β cyclodextrin nanosponges using a novel and efficient microwave mediated method for enhancing bioavailability of Rilpivirine HCl (RLP).

Significance: Belonging to BCS class II RLP has pH dependent solubility and poor oral bioavailability. However, a fatty meal enhances its absorption hence the therapy indicates that the dosage form be consumed with a meal. But then it becomes tedious and inconvenient to continue the therapy for years with having to face the associated gastric side effects such as nausea.

Method: Microwave synthesizer was used to mediate the poly-condensation reaction between β-cyclodextrin and cross-linker diphenylcarbonate. Critical parameters selected were polymer to cross-linker ratio, Watt power, reaction time and solvent volume. Characterization studies were performed using FTIR, DSC, SEM, ¹H-NMR and PXRD. Molecular modeling was applied to confirm the possibility of drug entrapment. In vitro drug dissolution followed by oral bioavailability studies was performed in Sprawley rats. Samples were analyzed using HPLC.

Results: Microwave synthesis yields para-crystalline, porous nanosponges (～205?nm). Drug entrapment led to enhancement of solubility and a two-fold increase in drug dissolution (P?C_max and AUC_0-∞ increases significantly (C_max of NS～ 586?±?5.91?ng/mL; plain RLP ～310?±?5. 74?ng/mL).

Conclusion: The approach offers a comfortable dosing zone for AIDs patients, negating the requirement of consuming the formulation in a fed state due to enhancement in drugs’ oral bioavailability.     

Crystal growth and structure of L-methionine L-methioninium hydrogen maleate—a new NLO material

Abstract

A new organic nonlinear optical (NLO) crystal from the amino acid family, viz., L-methionine L-methioninium hydrogen maleate (LMMM), has been grown by slow evaporation method from aqueous solution. Bulk crystals were grown using submerged seed solution method. The structure was elucidated using the single crystal x-ray diffraction data. The compound crystallized in the space group P2₁ and the unit cell contains a protonated L-methioninium cation and a zwitterionic methionine residue plus a maleate anion. The backbone conformation angles Ψ¹ and Ψ² are in cis and trans configurations for both the methionine and methioninium residues, respectively. Amino and carboxyl groups of the methioninium and methionine residues are connected through N–H…O hydrogen bonds leading to a ring R₂²(10) motif.     

Effect of Water and Solvent Selection on the SAFA Purification Times for Metallic Nitride Fullerenes

This paper addresses two key parameters in the SAFA purification method for isolating endohedral metallofullerenes. The percent water content in the reactive aminosilica significantly affects the time needed to isolate Sc₃N@I_h -C₈₀ metallic nitride fullerene (MNF). The role of solvent selection in the SAFA process is also discussed. The SAFA purification time needed for isolating Sc₃N@I_h -C₈₀ metallofullerene is influenced by the identity of the electron donating/accepting group on the aromatic solvent.     

Investigation of Composition of Endometallofullerene Extracts

Abstract

Gases evolved upon heating endometallofullerene (EMF) extracts with La or Y have been investigated. It has been shown that solvent molecules used to release EMF are observed in extracts up to high temperatures. It has been found that in the dimethylformamide (DMF) extract the EMF molecules are present mainly as the [EMF]^? anions, which were observed in electrospray mass spectra. The treatment of such extracts with iodine results in the anion reduction to neutral molecules.     

Synthesis of novel ultraviolet stabilizers based on [60]fullerene and their effects on photo-oxidative degradation of polystyrene

Abstract

Two N-benzyl fulleropyrrolidines were synthesized via Prato reaction. The polystyrene (PS) films containing 0.5?wt% fullerene and N-benzyl fulleropyrrolidines were prepared from toluene via the solvent evaporation method. The photo-oxidative activities and thermostability of these films were determined by monitoring the average molecular weight and thermogravimetric curve. The changes in weight loss (%) and tensile strength with irradiation time were also tracked. After 480?h of illumination, the weight loss of PS films was 6.8%, while the corresponding index of PS with C₆₀ was 6.1%. The weight loss of PS with two fulleropyrrolidines was significantly lower than that before (3.8% and 2.7%). The results manifested the good ultraviolet (UV) stabilizing effect and thermostability of these complex films compared with PS. A probable mechanism was proposed to account for the stabilizing action of the [60]fullerene derivatives as multifunctional UV stabilizers.     

Solvent Effects on the Resonance Raman Spectroscopy,Electronic Absorption Spectroscopy and Electrochemistry of Fullerenes and Fullerides

Abstract

The symmetry of C₆₀ and C₇₀ in solution is reduced by specific solvent effects, which have been studied in detail by electrochemistry, and electronic absorption and resonance Raman spectroscopies. This review outlines how surface/solvent interactions involving the fullerenes affects their physical properties.     

Fluorine self-diffusion in CaF2 and BaF2

The self-diffusion of F-18 in single crystals of BaF₂ and CaF₂ was measured between 350 and 940°C. The results were in agreement with diffusion coefficients deduced from ionic conductivity studies, and yieldedH's of 1,6 eV for BaF₂ and of 2.0 eV for CaF₂ for intrinsic diffusion. Below 700°C, extrinsic diffusion behaviour was observed in CaF₂ withH=0.9 eV. The formation energy for anion Frenkel defects was estimated to be in the range 2.2 to 3.1 eV. Both anion and cation diffusion rates were increased in CaF₂ doped with SmF₃ as compared with pure CaF₂, indicating an interrelation between anion and cation defects, as observed previously in the related substances, UO₂ and UO_2+x , The migration energy of cations was estimated to be roughly in the range 1.5±0.6 eV. The implications of the results in terms of diffusion mechanisms are discussed and the remaining uncertainties are indicated.Experiments performed in 1968 at CCR Euratom, Ispra, Italy. The present study constitutes part II of a study of fluorine self-diffusion. Part I is concerned with LiF and NaF (see ref. [6]).     

Environmentally benign novel green pigments: Pr1-xCaxPO4 (x = 0-0.4)

Rare earth based materials have recently attracted considerable attention as potential ecofriendly colourants for low temperature as well as high temperature applications. In the present study, we have synthesized a series of Ca-doped PrPO₄ compounds with the general formula, Pr_1-xCa_xPO₄ (x = 0-0.4 in steps of 0.1) and characterized the compounds by powder X-ray diffraction. All the compositions show a monoclinic monazite structure. The optical properties of the brilliantly coloured pigments [ L (brightness),a* (+ red- green),b* (+ yellow - blue) have been examined. These materials can find application as potential green colourants.