Enhanced direct electron transfer reactivity of hemoglobin in cationic gemini surfactant-room temperature ionic liquid composite film on glassy carbon electrodes

A novel composite film comprising cationic gemini surfactant butyl-α,ω-bis(dimethylcetylammonium bromide) (C₁₆H₃₃N(CH₃)₂-C₄H₈-N(CH₃)₂C₁₆H₃₃, C₁₆-C₄-C₁₆) and ionic liquid 1-octyl-3-methylimidazolium hexafluorophate (OMIMPF₆) has been prepared. The composite film shows good biocompatibility and it can promote the direct electron transfer between hemoglobin (Hb) and glassy carbon (GC) electrode. On the C₁₆-C₄-C₁₆ (dissolved in ethanol)-OMIMPF₆ film coated GC electrode, the immobilized Hb can exhibit a pair of well-defined, quasi-reversible and stable redox peaks with a formal potential of −0.317 V (vs SCE) in 0.10 M pH 7 phosphate buffer solutions. The electron transfer coefficient (α) of Hb is calculated to be 0.44 and the heterogeneous electron transfer rate constant is 6.08 s⁻¹. With the length of alkyl chains of gemini surfactant increasing and the ethanol concentration rising, the redox peaks of the resulting electrode C₁₆-C₄-C₁₆-OMIMPF₆-Hb/GC become bigger. The electrode presents good electrocatalytic response to peroxide hydrogen. The kinetic parameters I_max and k_m for the catalytic reaction are estimated. In addition, UV-vis spectra and reflectance absorption infrared spectra demonstrate that the Hb immobilized in the C₁₆-C₄-C₁₆-OMIMPF₆ film almost retains the structure of native Hb.     

Synthesis of a ruthenium complex of a cyclic trifunctional η6, η1, η1-arene–diphosphine ligand by intramolecular dehydrofluorinative carbon–carbon coupling

Treatment of the ruthenium complex cation [(η⁶-C₆H₃Me₃-1,3,5)(RuCl(dfppe)]⁺ {dfppe=(C₆F₅)₂PCH₂CH₂P(C₆F₅)₂} with proton sponge yields [{η⁶,η¹,η¹-C₆H₃Me-5-[CH₂-2-C₆F₄P(C₆F₅)CH₂]₂-1,3}RuCl]⁺ by stepwise intramolecular dehydrofluorinative carbon–carbon coupling.     

Steric effects of alkyl dibenzothiophenes: The root cause of frustrating efficacy of heterogeneous desulfurization for real diesel

High-carbon alkyl dibenzothiophenes (DBTs) in real diesel are difficult to remove. Their steric effect has been studied and identified as the controlling factor in heterogeneous catalytic oxidation desulfurization (ODS) process. Mixed alkyl DBTs (C₂-DBT, C₂-C₂-DBT, C₃-DBT, and C₃-C₃-DBT) were synthesized via DBT's Friedel–Crafts alkylation, and their reactivity is DBT > C₂-DBT > C₂-C₂-DBT > C₃-DBT > C₃-C₃-DBT. C₃-DBT, C₂-C₂-DBT, and C₃-C₃-DBT can be hardly removed by any of three efficient heterogeneous ODS processes, but are removed efficiently in a homogeneous ODS process of HAc-HPW-H₂O₂, which contrasts the great importance of their steric effects in heterogeneous catalytic process. Thus, the frustrating efficacy of various ODS processes for real diesel is likely originated from the unidentified high-carbon alkyl DBTs and their least reactivity in heterogeneous catalytic systems. And, the steric hindrance is diminished greatly in a homogeneous catalytic process. The results are instructive for the development of new catalysts and catalytic ODS processes for real diesel.     

Silyl group mediated linkage of closo-C2B10-cage to nido-C2B4-carborane: synthesis of the novel carborane ligand, 1-R-2-[5′-(SiMe2CH2)-2′,3′-(SiMe3)2-2′,3′-C2B4H5]-1,2-C2B10H10 (R=Me,Ph)

The reaction of the sodium salt of the monoanion, nido-[2,3-(Si(CH₃)₃)₂-2,3-C₂B₄H₅]⁻, with (chloromethyl)dimethylchlorosilane in a 1:1 molar ratio produced the B_(cage)-substituted cluster, nido-5-ClCH₂Si(CH₃)₂-2,3-(Si(CH₃)₃)₂-2,3-C₂B₄H₅ (1), in 81% yield. This product (1) was reacted further with the lithium salt of [closo-1-R-1,2-C₂B₁₀H₁₀]⁻ monoanion (R=Me, Ph) to give the novel linked and mixed C₂B₄/C₂B₁₀ carborane species, 1-Me-2-[5^′-SiMe₂CH₂-2^′,3^′-(SiMe₃)₂-2^′,3^′-C₂B₄H₅]-1,2-C₂B₁₀H₁₀ (2), 1-Ph-2-[5^′-SiMe₂CH₂-2^′,3^′-(SiMe₃)₂-2^′,3^′-C₂B₄H₅]-1,2-C₂B₁₀H₁₀ (3), in yields of 76% and 81%, respectively.     

Syntheses and Structures of Octamethylmetallocenes of Osmium

The reaction of sodium hexachloroosmate(IV) hydrate with five equivalents of tetramethylcyclopentadiene (C₅Me₄H₂) in refluxing ethanol yielded the novel coordination compound bis(tetramethylcyclopentadienyl)chloroosmocinium(IV) hexachloroosmate, [(η ⁵-C₅Me₄H)₂OsCl]₂[OsCl₆] (1). Compound 1 has been characterized by NMR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The cationic complex of 1 [(η ⁵-C₅Me₄H)₂OsCl]⁺, adopts a bent geometry with a ring centroid-osmium-ring centroid angle of 146.2° and an eclipsed conformation of its two tetramethylcyclopentadienyl rings. The addition of zinc powder to sodium hexachloroosmate(IV) hydrate and five equivalents of tetramethylcyclopentadiene in refluxing ethanol produced the known compound, bis(tetramethylcyclopentadienyl)osmium, (η ⁵-C₅Me₄H)₂Os (2). The crystal structure of 2 has been determined and it reveals an eclipsed arrangement of the tetramethylcyclopentadienyl rings in the solid state. The average Os–C_ring bond length in octamethylosmocene 2 (2.187 Å) is in accordance with corresponding bond lengths in osmocene, (η ⁵-C₅H₅)₂Os (2.19 Å) and decamethylosmocene, (η ⁵-C₅Me₅)₂Os (2.18 Å).     

New Long Chain Bases in Lipophosphonoglycan of Acanthamoeba Castellanii

The polymer called lipophosphonoglycan (LPG) was isolated from Acanthamoeba castellanii membranes after exhaustive delipidation and butanol extraction. A novel extremely long phytosphingosine was revealed in glycoinositolphosphosphingolipid (GIPSL). All data obtained by gas–liquid chromatography coupled with MS analyses of products liberated during acid methanolysis and products of sodium metaperiodate and permanganate–periodate oxidations showed an unusual pattern of long chain bases (LCB) with branched bases (anteiso-C₂₄, anteiso-C₂₅, anteiso-C₂₆, iso-C₂₆, anteiso-C₂₇, and anteiso-C₂₈) and normal ones (C₂₄, C₂₅, C₂₆, C₂₇). The phytosphingosines with hexa-, hepta-, and octacosanoic chains have not been detected in Acanthamoeba cells up to now. Also, the isomer configuration of long chain bases in LPG of A. castellanii was not defined in earlier reports. In the GC–MS chromatograms, the component forming a peak corresponding to anteiso-C₂₅ phytosphingosine was the most abundant and constituted more than 50 % of all LCB.     

Mechanical properties of C58 materials and their dependence on thermal treatment

C₅₈ fullerene cages made by electron-impact induced fragmentation of C₆₀ fullerenes have been assembled into several micron thick solid films by low energy cluster beam deposition onto inert substrates held at room temperature under ultrahigh vacuum. The resulting as-prepared material, RT-C₅₈, behaves as an amorphous wide-band semiconductor. Nanoindentation was used to measure its mechanical properties revealing that RT-C₅₈ has a higher elastic modulus E and hardness H than the reference carbon allotropes solid C₆₀ and Highly Ordered Pyrolytic Graphite (HOPG): E(RT-C₅₈) = 14 GPa and H(RT-C₅₈) = 1.2 GPa. This effect can be explained by the unique intrinsic “functionalization” of C₅₈ cages: they comprise reactive surface sites constituted by annelated pentagon rings which give rise to covalently stabilized oligomers, –C₅₈–C₅₈–C₅₈, under our deposition conditions. Annealing, thick RT-C₅₈ films up to 1100 K in ultrahigh vacuum results in HT-C₅₈, a new material with considerably modified electronic and vibrational properties compared to the as-prepared RT-C₅₈ film. The associated molecular transformations, including also partial cage–cage coalescence reactions, raise the overall mechanical hardness of the material: H(HT-C₅₈) = 3.9 GPa.     

Thermodynamic and structural analyses of the solid phases in multi-alkane mixtures similar to petroleum cuts at ambient temperature

Structural analyses were carried out by X-ray diffraction, at ambient temperature, on multi-alkane samples whose mole fraction distribution shows a shape of the ‘exponential decreasing’ type, as observed in petroleum cuts. Nine samples, whose normal-alkane number varies from 15 to 23, have been studied with mole fraction continuous distributions of normal-alkanes going from C₂₂-C₃₆ to C₁₄-C₃₆: each mixture differs from the previous sample by the addition of a lighter n-alkane. At the solid state, the multi-alkane solid samples C₂₂-C₃₆ and C₂₁-C₃₆ are two-phase, C₂₀-C₃₆ to C₁₅-C₃₆, three-phase, and the broader distribution C₁₄-C₃₆, four-phase. In these polyphase solid systems, whose heaviest n-alkane is always C₃₆, the average composition of the heavy and middle phases are constant and their structure are isostructural to the β′ ordered intermediate solid solution, observed in n-alkane binary or ternary molecular alloys; the mean carbon atom number of the light phase decreases as the global average carbon atom number of the synthetic mixtures in relation to the addition of light n-alkanes and its structure simultaneously evolves from the β′ ordered intermediate solid solution towards the β-RI(Fmmm) and the disordered solid solutions, observed in pure n-alkanes: the light n-alkane added between each distribution intercalates itself into the structure whose molecule stacking period (thickness) is compatible with its own carbon chain length, in order to reduce the molecular gaps.     

Adsorptive and stripping behavior of methylene blue at gold electrodes in the presence of cationic gemini surfactants

The adsorptive and stripping behavior of methylene blue (i.e. methylene blue chloride, MB) at a gold electrode has been studied with voltammetry, alternating current impedance spectra (ACIS) and quartz crystal microbalance (QCM). MB exhibits a pair of cyclic voltammetry peaks at about −0.3 V (versus SCE) in 0.05 M pH 6.9 phosphate buffer solutions. In the presence of cationic gemini surfactants such as C₁₆H₃₃N(CH₃)₂-C₄H₈-N(CH₃)₂C₁₆H₃₃Br₂ (C₁₆-C₄-C₁₆), C₁₆H₃₃N(CH₃)₂-C₄H₇OH-N(CH₃)₂C₁₆H₃₃Br₂ (C₁₆-C₄OH-C₁₆), C₁₆H₃₃N(CH₃)₂-CH₂-C₆H₄-CH₂-N(CH₃)₂C₁₆H₃₃Br₂ (C₁₆-ph-C₁₆) and C₁₆H₃₃N(CH₃)₂-C₁₂H₂₄-N(CH₃)₂C₁₆H₃₃Br₂ (C₁₆-C₁₂-C₁₆), the anodic peak grows rapidly and moves in positive direction, but the cathodic peak gradually decreases, due to the association adsorption and electrostatic interaction of the geminis with MB and its reduced product (i.e. leuko methylene blue, LMB). With the aid of geminis the adsorption amount of MB increases under open-circuit, but the impedance of the mixed adsorption film to Fe(CN)₆^3−/4− almost keeps unchanged, compared with either bare gold electrodes or MB film, while the adsorption film of geminis exhibits greater impedance. This probably is due to the electron medium action of MB in the film. Gemini surfactants with same alkyl-chain (i.e. -(CH₂)₁₅CH₃) but different molecular structure, exhibit different influence. The enhancing action of geminis studied follows such order as: C₁₆-ph-C₁₆ > C₁₆-C₄-C₁₆ > C₁₆-C₄OH-C₁₆ > C₁₆-C₁₂-C₁₆. The change of peak potential was ascribed to the interaction between MB and surfactants, as well as the blocking action of surfactant film. For comparison, the influence of dihexadecyldimethylammonium bromide (DCAB) and cetyltrimethylammonium bromide (CTAB) was studied, and the influence of other factors is discussed as well.     

A triheterometallic cluster: synthesis and structural characterisation of a cyclopentadienyl-substituted pentanuclear cluster based on an Os3CoRu metal core

The ionic coupling of the carbonyl cluster anion [Os₃Co(CO)₁₃]⁻ (1) with [Ru(η⁵-C₅H₅)(NCMe)₃]⁺ affords the new pentanuclear triheterometallic cluster Os₃CoRu(CO)₁₃(η⁵-C₅H₅) (2) as well as the known bimetallic cluster compounds HOs₃Ru(CO)₁₁(η⁵-C₅H₅) and Os₃Ru₂(CO)₁₁(η⁵-C₅H₅)₂. The crystal structure of cluster 2 shows that the metal framework is based on a trigonal bipyramid (approximate C_s symmetry) with the Ru, Co and an Os atom occupying the equatorial metal plane.     

The effects of fullerene (C60) crystal structure on its electrochemical capacitance

The electrochemical properties of different types of fullerene crystals (x-C₆₀), having hollow-long cylindrical (C-C₆₀), hollow-long square (S-C₆₀), and thick solid-short hexagonal (H-C₆₀) shapes were investigated. The prepared x-C₆₀ samples had specific dimensions with respect to aspect ratio (12.0, 6.7, and 1.5) and lattice spacing distance (1.12, 1.04, and 1.00 nm). Interestingly, it was possible to control the aspect ratio and lattice spacing distance by adjusting the molecular ratio of C₆₀ to the aromatic solvent (m-xylene) used in the preparation. In addition, the number of m-xylene molecule in the x-C₆₀ crystal structure increased with decreasing ratio of x-C₆₀ to m-xylene in the solution, corresponding to ca. C₆₀·0.83m-xylene (for C-C₆₀), C₆₀·0.39m-xylene (for S-C₆₀), and C₆₀·0.36m-xylene (for H-C₆₀). A more ordered arrangement of m-xylene molecules resulted in an improved electrochemical capacitance of x-C₆₀. Importantly, in the case of the regular structure (C-, S-, H-C₆₀), when m-xylene was assembled in the x-C₆₀ structure, the large lattice spacing distance increased. This explains why the C-C₆₀ sample had the largest electrochemical capacitance, compared to the S- and H-C₆₀ samples. Such a configuration would allow for a high charge accumulation and the formation of a donor-acceptor complex, which would permit an easier charge transfer.     

Solvent/C60 exchange on Ir(CO)(PPH3)2(Cl)(η2-C60) and solvent/solvent’ exchange on Ir(CO)(PPH3)2(Cl)(solvent)

Dissociation of C₆₀ from Ir(CO)(PPh₃)₂(Cl)(η²-C₆₀) in a binary mixture of solvents (solvent₁ and solvent₂) produced non-equilibrium mixtures of Ir(CO)(PPh₃)₂(Cl)(solvent₁) and Ir(CO)(PPh₃)₂(Cl)(solvent₂). Once the solvated species were produced, they underwent a relative fast solvent exchange between them to produce an equilibrium mixture.     

Surface Adsorption and Aggregation Properties of Novel l-Lysine-Based Gemini Surfactants

Four chiral l-lysine-based gemini surfactants with different spacers were synthesized, namely, disodium (18R,23R)-12,20,21,29-tetraoxo-13,19,22,28-tetraazatetracontane-18,23-dicarboxylate([C₁₂-2-C₁₂]Na₂), disodium (18R,25R)-12,20,23,31-tetraoxo-13,19,24,30-tetraazadotetracontane-18,25-dicarboxylate([C₁₂-4-C₁₂]Na₂), disodium(18R,27R)-12,20,25,33-tetraoxo-13,19,26,32-tetraazatetratetracontane-18,27-dicarboxylate([C₁₂-6-C₁₂]Na₂), disodium(2R,2′R)- 2,2′-(6-chloro-1,3,5-triazine-2,4-diyl)bis(azanediyl)bis(6-dodecanamidohexanoate) ([C₁₂-T-C₁₂]Na₂). The chemical structures of the prepared compounds were confirmed by ¹H-NMR, ESI–MS and IR spectra. Further, the critical micelle concentration (CMC) of these surfactants in aqueous solutions was determined by surface tension and conductometry methods at 25 °C. Moreover, the adsorption and micellization behaviors of these surfactants were estimated by pC₂₀, the minimum average area per surfactant molecule (A_min), and standard free energy for micellization and adsorption ( \( \Updelta G_{\text{mic}}^{^\circ } \) and \( \Updelta G_{\text{ads}}^{^\circ } \) ). The results show that the four gemini surfactants have low CMC values and significantly low surface tension. Furthermore, the surfactants show strong adsorption at the air–water interface. The CMC and A_min values of the surfactants were found to be in the order of [C₁₂-2-C₁₂]Na₂ < [C₁₂-4-C₁₂]Na₂ < [C₁₂-6-C₁₂]Na₂ < [C₁₂-T-C₁₂]Na₂, which were in agreement with the sequence of \( \Updelta G_{\text{mic}}^{^\circ } \) and \( \Updelta G_{\text{ads}}^{^\circ } \) . The circular dichroism of the surfactants indicated the formation of chiral aggregates above the CMC values.     

Isolation and identification of constituents of Jasminum auriculatum (Vahl) leaves

Jasminum auriculatum (Vahl) (family: Malvaceae) widely grown in India was analysed for its fatty acids and waxy constituents. Straight-chain hydrocarbons (C₂₀-C₃₄), fatty acids (C₁₄-C₂₃) and fatty alcohols (C₂₁-C₃₂) were found in the 95% aqueous ethanol extract of the leaves of the plant. Malvalic acid was the only cyclic acid identified. Hydrocarbons (C₂₉ and C₃₁), fatty acids (C₁₆, C₁₈, C_18:1, C_18:2, C_18:3 and C₂₂) and fatty alcohols (iso-C₂₆, C₂₈ and C₃₀) were the major components. Four polyalcohols, namely D-mannitol, xylitol, inositol and sorbitol, have also been found in the alcoholic extract of the leaves.     

Synthesis and properties of pyrene-functionalized polyacetylene. A stable helical polymer emitting fluorescence

Pyrene-functionalized chiral N-propargylamide, (R)-HC≡CCH₂NHCOCH(CH₃)O-1,4-C₆H₄-OCO(CH₂)₃-1-pyrenyl (1) was polymerized with (nbd)Rh⁺[η⁶-C₆H₅B⁻(C₆H₅)₃] as a catalyst to obtain the corresponding polymer with a moderate weight in a good yield. Poly(1) was soluble in CHCl₃, CH₂Cl₂, and THF. The polarimetric and CD spectroscopic data indicated that poly(1) existed in a helical structure with predominantly one-handed screw sense in these solvents. The helical structure was stable upon heating and addition of MeOH. Poly(1) showed very large excimer-based fluorescence compared with 1.     

Aliphatic,Isoprenoid and Aromatic Acids from an Israeli Shale

Normal fatty acids (C₉-C₁₉); isoprenoid acid (C₁₀); aromatic acids (C₁₁-C₁₃) of the general formula C_nH_{2 n-8} O₂, and two aromatic acids (C₁₁, C₁₂) of the formula C_nH_{2 n-14} O₂, were identified in a bitumen obtained from shale of Nebi Musa (near Jericho), using chromatographic (GLC) and spectroscopic (MS) methods.     

Metallacarboranes as an anion and a cation in a single species: a unique example for ion pairs

The reaction of closo-exo-5,6-Na(THF)₂-1-Na(THF)₂-2,4-(SiMe₃)₂-2,4-C₂B₄H₄ (1) with anhydrous NdCl₃, in a molar ratio of 2:1, produced the full-sandwiched neodymacarborane, 2,2^′,4,4^′-(SiMe₃)₄-5,6-[(μ-H)₂Na(THF)₂]-1,1^′-commo-Nd(η⁵-2,4-C₂B₄H₄)₂ (2), as a yellow-green crystalline solid in 80% yield. Compound 2 was further reacted with NdCl₃, in 3:1 molar ratio, in a solvent mixture of dry benzene and THF to produce, in 75% yield, the novel dimeric ion-pair, {[closo-1-Nd(μ-H)₆-2,4-(SiMe₃)₂-2,4-C₂B₄H₄]⁺[1,1^′-(THF)₂-2,2^′,4,4^′-(SiMe₃)₄-5,5^′,6,6^′-(μ-H)₄-1,1^′-commo-Nd(η⁵-2,4-C₂B₄H₄)]⁻(C₄H₈O)(C₆H₆)₂}₂ (3), consisting of a half-sandwich cationic neodymacarborane that is coordinated to anionic full-sandwiched neodymacarborane. Thus, a dual role of metallacarboranes as both the cation and the anion in a single species has been exemplified.     

Scientific foundations of preparation and technologies of production of the catalysts of reforming of gasoline fractions: Development of the process technology

The article summarizes the results of development of the scientific foundations of preparation of the catalysts, and of the experimental development works on creation of the new technologies of their production with the use of physical models, which were previously created on the basis of fundamental research. The results of the adoption of the new production technologies of the reforming catalysts of the PR series at the domestic plants are presented. The adoption consisted in creation and approbation of the fundamentally new technologies of production of the aluminum hydroxide (AHO) by means of the continuous method, modification of AHO by the elements of IV group, plasticization and forming of AHO in the production of the support, application of H₂PtCl₆ using the reactions of the ligand substitution of C⁻ by the functional groups of the support, and reduction and activation of the catalyst, which provide the optimal chemical com- position. Their operation during the 15-year period is analyzed. The reasons of high selectivity (up to 90%) of the new catalysts are found; the new technologies of the combined processing of mixture of C₃-C₄ alkanes with C₅₊ are developed and tested for the production of the high-octane catalysts with selectivity approaching 100%. The main effect of the C₅₊ yield increase of the end products is achieved by the transformation of the C₃-C₄ alkanes into the more high-molecular aromatic hydrocarbons. New processes of the combined processing of the mixtures of C₃-C₄ and gasoline fractions can be considered to be an alternative technology, which solves the important task of broadening the source of raw materials of the motor fuels by the inclusion of the C₃-C₄ alkanes of little value into the processing.     

Syndiospecific styrene polymerization by (tert-BuC5H4)TiCl2(O-2,6-iPr2C6H3) – borate catalyst system

(^tBuC₅H₄)TiCl₂(O-2,6-ⁱPr₂C₆H₃) (2) exhibited relatively high catalytic activity for syndiospecific polymerization of styrene at 25 °C if both [PhMe₂NH]B(C₆F₅)₄ and a mixture of AlⁱBu₃/Al(n-C₈H₁₇)₃ were used as the cocatalyst. Effects of both organoaluminum and organoboron compounds were explored, and the effect of cocatalyst was different from that observed in 1-hexene polymerization catalyzed by Cp*TiCl₂(O-2,6-ⁱPr₂C₆H₃) (1). Resultant syndiotactic polystyrene possessed narrow molecular weight distribution under the optimized conditions, and the M_w values were unchanged during the time course.     

Synthesis of isoalkanes over Fe–Zn–Zr/HY composite catalyst through carbon dioxide hydrogenation

The reaction path of isoalkanes formation via CO₂ hydrogenation was studied over the Fe–Zn–Zr/HY composite catalyst, which gives high selectivity to isoalkanes. The results indicate that the reverse water–gas shift reaction is not the indispensable step for the synthesis of hydrocarbons. And i-C₄ (iso-butane) is formed from propylene and methanol through MTG (methanol to gasoline) reaction and i-C₅ (iso-pentane) obtained from the reaction of C₂ and C₃ through the additive dimerization. A part of C₁, C₄ is formed on the sole Fe–Zn–Zr catalyst from methanol for the CO₂ hydrogenation over Fe–Zn–Zr/HY composite catalyst.