Detection and characterization of structural changes in the hard-disk fluid under freezing and melting conditions

The fluid of two-dimensional hard disks is investigated over a range of densities by Monte Carlo simulations in order to detect and characterize structural changes which take place when the condition of freezing and melting is approached. A novel method is proposed based on the use of the Voronoi tessellation and a certain shape factor which turns out to be a clear indicator of the presence of different underlying substructures (domains). Close to the freezing condition the probability distribution of the shape factor develops a second distinct maximum corresponding to a predominant presence of near-regular hexagons, whereas the original peak, having its origin primarily in pentagons and distorted hexagons, diminishes and disappears at melting density.     

Influence of two grinding methods on the uncertainty of determinations of heavy metals in atomic absorption spectrometry/electrothermal atomisation of plant samples

 Chemical analyses of trace elements are affected by relatively high analytical errors due to the different steps of the laboratory procedures: samples grinding, mineralisation and instrumental measurements. In the present communication, the influence of the grinding phase on the global uncertainty of Pb, Cd, Ni and Cr determinations in plant samples by the classical method of atomic absorption spectrometry/electrothermal atomisation (AAS-ETA) after dry ashing is quantified. Two grinding machines, a planetary mill with balls and jars of agate versus a stainless steel grinder were compared by analysing leaf samples of cucumber, strawberry, kiwivines, apple trees and grapevines from agricultural experimental plots under controlled conditions. Variance components due to the difference between grinding methods and experimental plots were estimated. Further, the simultaneous effects of the grinding methods on all considered metals have been evaluated by analysis of variance. With the stainless steel grinder, on average, higher levels of the considered heavy metals were obtained (up to 67% of the mean values). On average, the increments were similar for metals contained in steel (Ni and Cr) and those not contained (Pb and Cd). The true causes of these differences need further investigation to determine whether the higher metal detection is due to possible contamination, to a different grinding quality or to other reasons. Finally, the grinding methods did not seem to affect the combined uncertainty of the analyses. Received: 3 November 1997 · Accepted: 29 November 1997     

Dual catalytic performance of arene-ruthenium amine complexes for norbornene ring-opening metathesis and methyl methacrylate atom-transfer radical polymerizations

Arene ruthenium(II) complexes bearing the cyclic amines RuCl₂(η⁶-p-cymene)(pyrrolidine)] ( 1 ), [RuCl₂(η⁶-p-cymene)(piperidine)] ( 2 ), and [RuCl₂(η⁶-p-cymene)(peridroazepine)] ( 3 ) were successfully synthesized. Complexes 1 – 3 were fully characterized by means of Fourier transform infrared, UV–visible, and NMR spectroscopy, elemental analysis, cyclic voltammetry, computational methods, and one of the complexes was further studied by single crystal X-ray crystallography. These compounds were evaluated as catalytic precursors for ring-opening metathesis polymerization (ROMP) of norbornene (NBE) and atom-transfer radical polymerization (ATRP) of methyl methacrylate (MMA). NBE polymerization via ROMP was evaluated using complexes 1 – 3 as precatalysts in the presence of ethyl diazoacetate (EDA) under different [NBE]/[EDA]/[Ru] ratios, temperatures (25 and 50°C), and reaction times (5–60 min). The highest yields of polyNBE were obtained with [NBE]/[EDA]/[Ru] = 5000/28/1 for 60 min at 50°C. MMA polymerization via ATRP was conducted using 1 – 3 as catalysts in the presence of ethyl-α-bromoisobutyrate (EBiB) as initiator. The catalytic tests were evaluated as a function of the reaction time using the initial molar ratio of [MMA]/[EBiB]/[Ru] = 1000/2/1 at 95°C. The increase in molecular weight as function of time indicates that complexes 1–3 were able to mediate the MMA polymerization with an acceptable rate and some level of control. Differences in the rate of polymerization were observed in the order 3 > 2 > 1 for the ROMP and ATRP.     

Facile Synthesis of 1,2-Disubstituted Benzimidazoles Usingp-Toluenesulfonic Acid through Grinding Method

Russian Journal of Organic Chemistry - An efficient synthetic method for the highly selective synthesis of pharmacologically active 1,2-disubstituted benzimidazole derivatives...     

Adamantyl ferrocene derivatives: Antioxidant abilities and effects on model lipid membranes

A series of homoannularly and heteroannularly substituted adamantyl ferrocene derivatives has been synthesized and their effects on membrane fluidity were investigated using liposomes as the membrane models. The liposome formulations of adamantyl ferrocene derivatives were characterized by using dynamic light scattering, differential scanning calorimetry and fluorescence anisotropy measurements. It was demonstrated that adamantyl ferrocene derivatives incorporated into the liposome significantly affect the structure of the lipid bilayer. The results of the study have revealed that adamantyl ferrocene derivatives, compounds 9 – 12, partition into the hydrophobic/hydrophilic interface of the membrane, causing a significant decrease in membrane fluidity. The antioxidant potential of synthesized compounds was assessed with DPPH method and it was shown that the examined compounds possess certain antioxidant activity.