Characterization of the active site in the thiocyanate-forming protein from Thlaspi arvense (TaTFP) using EPR spectroscopy.

Glucosinolates are plant thioglucosides, which act as chemical defenses. Upon tissue damage, their myrosinase-catalyzed hydrolysis yields aglucones that rearrange to toxic isothiocyanates. Specifier proteins such as thiocyanate-forming protein from Thlaspi arvense (TaTFP) are non-heme iron proteins, which capture the aglucone to form alternative products, e.g. nitriles or thiocyanates. To resolve the electronic state of the bound iron cofactor in TaTFP, we applied continuous wave electron paramagnetic resonance (CW EPR) spectroscopy at X-and Q-band frequencies (∼9.4 and ∼34 GHz). We found characteristic features of high spin and low spin states of a d 5 electronic configuration and local rhombic symmetry during catalysis. We monitored the oxidation states of bound iron during conversion of allylglucosinolate by myrosinase and TaTFP in presence and absence of supplemented Fe2+. Without added Fe2+, most high spin features of bound Fe3+ were preserved, while different g'-values of the low spin part indicated slight rearrangements in the coordination sphere and/or structural geometry. We also examined involvement of the redox pair Fe3+/Fe2 in samples with supplemented Fe2+. The absence of any EPR signal related to Fe3+ or Fe2+ using an iron-binding deficient TaTFP variant allowed us to conclude that recorded EPR signals originated from the bound iron cofactor.

1-Ethyl-3-methylimidazolium Acetate as a Reactive Solvent for Elemental Sulfur and Poly(sulfur nitride).

We investigate the reactive dissolution process of poly(sulfur nitride) (SN)x in the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate [EMIm][OAc] in comparison to the process of elemental sulfur in the same IL. It has been known from the literature that during the reaction of S8 with [EMIm][OAc], the respective thione is formed via a radical mechanism. Here, we present new results on the kinetics of the formation of the respective imidazole thione (EMImS) via the hexasulfur dianion [S6]2- and the trisulfur radical anion [S3]•-. We can show that [S6]2- is formed first, which dissociates then to [S3]•-. Also, long-term stable radicals occur, which are necessary side products provided in a reaction scheme. During the reaction of [EMIm][OAc] with (SN)x chains, two further products can be identified, one of which is the corresponding imine. The reactions are followed by time-resolved NMR spectroscopic methods that showed the corresponding product distributions and allowed the assignment of the individual signals. In addition, continuous-wave (CW) EPR and UV/vis spectroscopic measurements show the course of the reactions. Another significant difference in both reactions is the formation of a long-term stable radical in the sulfur-IL system, which remains active over 35 days, while for the (SN)x-IL system, we can determine a radical species only with the spin trap 5,5-dimethyl-1-pyrrolin-N-oxide, which indicates the existence of short-living radicals. Since the molecular dynamics are restricted based on the EPR spectra, these radicals must be large.

Structure and reactivity of a mononuclear gold(II) complex.

Mononuclear gold(II) complexes are very rare labile species. Transient gold(II) species have been suggested in homogeneous catalysis and in medical applications, but their geometric and electronic structures have remained essentially unexplored: even fundamental data, such as the ionic radius of gold(II), are unknown. Now, an unprecedentedly stable neutral gold(II) complex of a porphyrin derivative has been isolated, and its structural and spectroscopic features determined. The gold atom adopts a 2+2 coordination mode in between those of gold(III) (four-coordinate square planar) and gold(I) (two-coordinate linear), owing to a second-order Jahn-Teller distortion enabled by the relativistically lowered 6s orbital of gold. The reactivity of this gold(II) complex towards dioxygen, nitrosobenzene and acids is discussed. This study provides insight on the ionic radius of gold(II), and allows it to be placed within the homologous series of nd9 Cu/Ag/Au divalent ions and the 5d8/9/10 Pt/Au/Hg 'relativistic' triad in the periodic table.

High-yield synthesis of a unique Mn(iii) siloxide complex through KMnO4 oxidation of a Mn(ii) precursor.

A unique trivalent manganese siloxide complex, blue-violet MnIIILi2Cl[(Ph2SiO)2O]2(THF)4·2THF (3) has been prepared by a straightforward two-step synthetic protocol. Lithiation of (Ph2SiOH)2O (1) followed by reaction with MnCl2(THF)2 gave the structurally remarkable Mn(ii) precursor MnIILi4Cl2[(Ph2SiO)2O]2(THF)5·2THF (2). Surprisingly, the final oxidation step could be achieved using KMnO4 in THF to provide the Mn(iii) species 3 in high yield (91%). Both title compounds were structurally characterized by single-crystal X-ray diffraction.

The solvation study of carbon, silicon and their mixed nanotubes in water solution.

Nanotubes are believed to open the road toward different modern fields, either technological or biological. However, the applications of nanotubes have been badly impeded for the poor solubility in water which is especially essential for studies in the presence of living cells. Therefore, water soluble samples are in demand. Herein, the outcomes of Monte Carlo simulations of different sets of multiwall nanotubes immersed in water are reported. A number of multi wall nanotube samples, comprised of pure carbon, pure silicon and several mixtures of carbon and silicon are the subjects of study. The simulations are carried out in an (N,V,T) ensemble. The purpose of this report is to look at the effects of nanotube size (diameter) and nanotube type (pure carbon, pure silicon or a mixture of carbon and silicon) variation on solubility of multiwall nanotubes in terms of number of water molecules in shell volume. It is found that the solubility of the multi wall carbon nanotube samples is size independent, whereas multi wall silicon nanotube samples solubility varies with diameter of the inner tube. The higher solubility of samples containing silicon can be attributed to the larger atomic size of silicon atom which provides more direct contact with the water molecules. The other affecting factor is the bigger inter space (the space between inner and outer tube) in the case of silicon samples. Carbon type multi wall nanotubes appeared as better candidates for transporting water molecules through a multi wall nanotube structure, while in the case of water adsorption problems it is better to use multi wall silicon nanotubes or a mixture of multi wall carbon/ silicon nanotubes.