Preparative isolation of (+)-beta-eudesmol fromAmyris balsamifera

Summary Optically pure (+)-beta-eudesmol is a possible starting material for the synthesis of several termite defense compounds. A two step procedure for the isolation of gram quantities of (+)-beta-eudesmol from commercially availableAmyris balsamifera oil (syn. West Indian sandalwood oil), containing 8% beta-eudesmol, was developed. Step one consisted of an efficient vacuum distillation of the total oil. Step two was a medium pressure LC separation with an AgNO₃ impregnated silica gel stationary phase. Several other separation procedures failed due to the presence of many closely related sesquiterpene alcohols (75% of the oil).     

Multiple-steering QM-MM calculation of the free energy profile in chorismate mutase

A novel technique for computing free energy profiles in enzymatic reactions using the multiple steering molecular dynamics approach in the context of an efficient QM-MM density functional scheme is presented. The conversion reaction of chorismate to prephenate catalyzed by the Bacillus subtilis enzyme chorismate mutase has been chosen as an illustrative example.     

Simulation of mesogenic diruthenium tetracarboxylates: Development of a force field for coordination polymers of the MMX type

A classical molecular mechanics force field, able to simulate coordination polymers (CP) based on ruthenium carboxylates (Ru₂(O₂CR_eq)₄L_ax) (eq = equatorial group containing aliphatic chains, L_ax= axial ligand), has been developed. New parameters extracted from experimental data and quantum calculations on short aliphatic chains model systems were included in the generalized AMBER force field. The proposed parametrization was evaluated using model systems with known structure, containing either short or long aliphatic chains; experimental results were reproduced satisfactorily. This modified force field, although in a preliminary stage, could then be applied to long chain liquid crystalline compounds. The resulting atomistic simulations allowed assessing the relative influence of the factors determining the CP conformation, determinant for the physical properties of these materials. © 2013 Wiley Periodicals, Inc.     

Deformability of thermoplastics in physiological salt solution

Conclusions 1. The creep of thermoplastics in physiological salt solution is characterized by change in the rate of creep deformation relative to the creep in air. The bending creep deformations of HMWPE and phenylone and the compressive creep deformation of HMWPE are described by a binomial equation [Eq. (5)] and the compressive creep deformation of phenylone is described by Eq. (6).2. The lifetime of the thermoplastics studied under static compression and bending determined relative to limiting deformations is described by Eq. (7). Under the same stresses and limiting deformations, the lifetime of phenylone in physiological salt solution is greater than the lifetime of HMWPE.3. After the simultaneous action of physiological salt solution and static stress over one month, most of the characteristics of short-term strength in phenylone are significantly reduced due to swelling in the model medium.Paper presented at the Third All-Union Conference on Polymer Mechanics, Riga, 1976.N. N. Priorov Central Scientific-Research Institute of Traumatology and Orthopedics, Moscow. Kazan Construction Engineering Institute. Translated from Mekhanika Polimerov, No. 2, pp. 325–331, March–April, 1978.     

Energy transfer in the nanostar: the role of coulombic coupling and dynamics

We present a theoretical investigation of energy transfer in the phenylene ethynelene dendrimer known as the nanostar. Data from extensive molecular dynamics simulations are used to model the dynamical effects caused by torsional motion of the phenyl groups. We compare rate constants for energy transfer between the two-ring chromophore and the three-ring chromophore obtained via the F?rster model, the ideal dipole approximation (IDA), and the transition density cube (TDC) method, which has as its limit an exact representation of the Coulombic coupling. We find that the rate constants obtained with the TDC are extremely sensitive to the phenyl group rotation, whereas the constants computed with the F?rster model and the IDA are not. The implications of these results for the interpretation of recent pump-probe experiments on the nanostar are discussed in detail. Finally, we predict the temperature dependence of the rate constant for energy transfer.