Reversible grafting of α-naphthylmethyl radicals to epitaxial graphene

The Kolbe electrochemical oxidation strategy has been utilized to achieve an efficient quasireversible electrochemical grafting of the α-naphthylmethyl functional group to graphene. The method facilitates reversible bandgap engineering in graphene and preparation of electrochemically erasable organic dielectric films. The picture shows Raman D-band maps of both systems.     

A remarkable anion effect on palladium nanoparticle formation and stabilization in hydroxyl-functionalized ionic liquids

Pd nanoparticles (NPs) with a small size and narrow size distribution were prepared from the decomposition of Pd(OAc)(2) in a series of hydroxyl-functionalized ionic liquids (ILs) comprising the 1-(2'-hydroxylethyl)-3-methylimidazolium cation and various anions, viz. [C(2)OHmim][OTf] (2.4 ± 0.5 nm), [C(2)OHmim][TFA] (2.3 ± 0.4 nm), [C(2)OHmim][BF(4)] (3.3 ± 0.6 nm), [C(2)OHmim][PF(6)] (3.1 ± 0.7 nm) and [C(2)OHmim][Tf(2)N] (4.0 ± 0.6 nm). Compared with Pd NPs isolated from the non-functionalized IL, [C(4)mim][Tf(2)N] (6.2 ± 1.1 nm), it would appear that the hydroxyl group accelerates the formation of the NPs, and also helps to protect the NPs from oxidation once formed. Based on the amount of Pd(OAc)(2) that remains after NP synthesis (under the given conditions) the ease of formation of the Pd NPs in the [C(2)OHmim](+)-based ILs follows the trend [Tf(2)N](-), [PF(6)](-) > [BF(4)](-) > [OTf](-) > [TFA](-). Also, the ability of the [C(2)OHmim](+)-based ILs to prevent the Pd NPs from undergoing oxidation follows the trend [Tf(2)N](-) > [PF(6)](-) > [TFA](-) > [OTf](-) > [BF(4)](-). DFT calculations were employed to rationalize the interactions between Pd NPs and the [C(2)OHmim](+) cation and the various anions.     

Electro-catalytic oxidative cleavage of lignin in a protic ionic liquid

Lignin is a component of lignocellulosic biomass and a promising matrix for recovering important renewable aromatic compounds. We present a new approach of electro-oxidative cleavage of lignin, dissolved in a special protic ionic liquid, using an anode with particular electro-catalytic activity. As appropriate ionic liquid triethylammonium methanesulfonate was identified, synthesised, explored for dissolution of alkali-lignin and used for electrolysis of 5 wt.% lignin solutions. As appropriate anode material, oxidation-stable ruthenium-vanadium-titanium mixed oxide electrodes were prepared and explored for their electro-catalytic activity. The electrolysis was performed at several potentials in the range from 1.0 V to 1.5 V (vs. an Ag pseudo reference electrode). A wide range of aromatic fragments was identified as cleavage products by means of GC-MS and HPLC measurements.     

The enthalpies of vaporisation of ionic liquids: new measurements and predictions

The enthalpies of vaporisation, Δ(vap)H(298), of seven ionic liquids (ILs) (four imidazoliums, a pyridinium, a phosphonium and an isouronium) have been determined by temperature programmed desorption using line of sight mass spectrometry. They were: 1-ethyl-3-methylimidazolium bis(pentafluoroethyl)phosphinate, [C(2)C(1)Im][PO(2)(C(2)F(5))(2)]; 1-butyl-3-methylimidazolium octylsulfate, [C(4)C(1)Im][C(8)OSO(3)]; 1-butyl-3-methylimidazolium tetrafluoroborate, [C(4)C(1)Im][BF(4)]; 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [C(6)C(1)Im][FAP]; 1-butylpyridinium methylsulfate, [C(4)Py][C(1)OSO(3)]; trihexyl(tetradecyl)phosphonium tetrafluoroborate, [P(6,6,6,14)][BF(4)] and O-ethyl-N,N,N',N'-tetramethylisouronium trifluoromethanesulfonate, [C(2)(C(1))(4)iU][TfO]. The values were found to be consistent with a previously proposed, predictive, model in which Δ(vap)H(298) is decomposed into a Coulombic component (computable from the IL density) and van der Waals components from the anion and cation. Two previously predicted values of Δ(vap)H(298) were found to be within 6 kJ mol(-1) of the measured experimental values. Values for the van der Waals components are tabulated for eleven cations and twelve anions. Predictions are made for Δ(vap)H(298) for 13 ILs with as yet unmeasured Δ(vap)H(298) values (using experimental molar volumes), and for a further 44 ILs using estimated molar volumes.     

Polytypism and oxo-tungstate polyhedra polymerization in novel complex uranyl tungstates

Three new uranyl tungstates, α-, β-Cs(2)[(UO(2))(2)(W(2)O(9))], and Rb(6)[(UO(2))(7)(WO(5))(2)(W(3)O(13))O(2)], have been obtained by high temperature solid state reactions. All three compounds display novel structure topologies: α- and β-Cs(2)[(UO(2))(2)(W(2)O(9))] are based upon layers with a new topology that can be related to the uranophane topology; Rb(6)[(UO(2))(7)(WO(5))(2)(W(3)O(13))O(2)] is a rare example of a non-molecular inorganic phase with layers containing oxo-tungstate trimers. The structural relationship between α- and β-Cs(2)[(UO(2))(2)(W(2)O(9))] can be assigned to polytypism.     

Monoclinic honeycomb-layered compound Li3Ni2SbO6: preparation, crystal structure and magnetic properties

Two synthetic routes-ion-exchange preparation from layered Na(3)Ni(2)SbO(6) at 300 °C and direct solid-state synthesis at 1150 °C resulted in layered Li(3)Ni(2)SbO(6), a cation-ordered derivative from the rocksalt type. The Fddd form reported earlier could not be reproduced. According to the XRD Rietveld analysis, Li(3)Ni(2)SbO(6) is a pseudohexagonal monoclinic structure, C2/m, with a = 5.1828(2) ?, b = 8.9677(3) ?, c = 5.1577(2) ?, β = 109.696(2)°. No Li/Ni mixed occupancy was detected. At high temperatures, the magnetic susceptibility follows the Curie-Weiss law with a positive value of Weiss temperature, ～8 K, indicating a predominance of ferromagnetic interactions. However, Li(3)Ni(2)SbO(6) orders antiferromagnetically at T(N)～ 15 K. The effective magnetic moment is 4.3 μ(B)/f.u. which satisfactorily agrees with theoretical estimations assuming high-spin configuration of Ni(2+) (S = 1). Electron spin resonance (ESR) spectra show single Lorentzian shape line attributed to Ni(2+) ion in octahedral coordination. The absorption is characterized by isotropic temperature independent effective g-factor g = 2.150 ± 0.005. In accordance with the layered honeycomb crystal structure determined for Li(3)Ni(2)SbO(6), the superexchange interaction between Ni(2+) ions through Ni-O-Ni pathways within Ni(2)SbO(6) layers are assumed to be ferromagnetic, while the dominant interaction between layers is antiferromagnetic.     

Luminescent heterometallic gold-copper alkynyl complexes stabilized by tridentate phosphine

The reactions between trinuclear gold complex tppmAu(3)Cl(3) (tppm = tris(diphenylphosphino)methane), arylacetylenes HC(2)C(6)H(4)X and Cu(+) under basic conditions result in formation of the heterometallic complexes [tppm(AuC(2)C(6)H(4)X)(3)Cu](+), X = H (1), COOMe (2), CN (3), OMe (4), NH(2) (5). These compounds belong to one structural motif and consist of the heterometallic {(AuC(2)C(6)H(4)X)(3)Cu} core stabilized by the tridentate phosphine. Compounds 1-5 were characterized by polynuclear NMR and IR spectroscopy, ESI-MS and single-crystal X-ray analysis. Luminescence properties of these complexes have been studied and revealed a substantial red shift of the emission maxima with the increase in the electron donicity of the alkynyl ligands substituents in the 550-680 nm range. The theoretical calculations of the electronic structures showed that variations of the substituents on the alkynyl ligands display very little effect on the molecular structural parameters but show appreciable influence on the orbital energies and luminescence characteristics of the compounds under study.     

Lewis base mediated autoionization of GeCl2 and SnCl2

Cationic and anionic species of heavier low-valent group 14 elements are intriguing targets in main group chemistry due to their synthetic potential and industrial applications. In the present study, we describe the synthesis of cationic (MCl(+)) and anionic (MCl(3)(-)) species of heavier low-valent group 14 elements of germanium(II) and tin(II) by using the substituted Schiff base 2,6-diacetylpyridinebis(2,6-diisopropylanil) as Lewis base (LB). Treatment of LB with 2 equiv of GeCl(2)·dioxane and SnCl(2) in toluene gives compounds [(LB)Ge(II)Cl](+)[Ge(II)Cl(3)](-) (1) and [(LB)Sn(II)Cl](+)[Sn(II)Cl(3)](-) (2), respectively, which possess each a low-valent cation and an anion. Compounds 1 and 2 are well characterized with various spectroscopic methods and single crystal X-ray structural analysis.     

Raman spectroscopy and imaging: applications in human breast cancer diagnosis

The applications of spectroscopic methods in cancer detection open new possibilities in early stage diagnostics. Raman spectroscopy and Raman imaging represent novel and rapidly developing tools in cancer diagnosis. In the study described in this paper Raman spectroscopy has been employed to examine noncancerous and cancerous human breast tissues of the same patient. The most significant differences between noncancerous and cancerous tissues were found in regions characteristic for the vibrations of carotenoids, lipids and proteins. Particular attention was paid to the role played by unsaturated fatty acids in the differentiation between the noncancerous and the cancerous tissues. Comparison of Raman spectra of the noncancerous and the cancerous tissues with the spectra of oleic, linoleic, α-linolenic, γ-linolenic, docosahexaenoic and eicosapentaenoic acids has been presented. The role of sample preparation in the determination of cancer markers is also discussed in this study.