Synthesis of Tenuilobine,a Bis-polyamine Alkaloid from Oncinotis tenuiloba,and Its Transamidation to Isotenuilobine

From the leaves of Oncinotis tenuiloba STAPF , a novel polyamine alkaloid, tenuilobine ( 9 ), was isolated. This paper presents the synthesis of 9 , as well as the base-catalyzed Zip reaction of 9 , leading to the transamidation product isotenuilobine ( 10 ). The structure of 10 was further confirmed by 2D-NMR correlation spectroscopy. For analytical purposes, the bis-polyamines 9 and 10 were converted into their pentaacetyl derivatives 12 and 11 , respectively, which were readily separable by reverse-phase HPLC.     

Mass spectrometric studies of potent inhibitors of farnesyl protein transferase--detection of pentameric noncovalent complexes

Farnesyl protein transferase (FPT) inhibition is an interesting and promising approach to noncytotoxic anticancer therapy. Research in this area has resulted in several orally active compounds that are in clinical trials. Electrospray ionization (ESI) time-of-flight mass spectrometry (TOF-MS) was used for the direct detection of a 95 182 Da pentameric noncovalent complex of alpha/beta subunits of FPT containing Zn, farnesyl pyrophosphate (FPP) and SCH 66336, a compound currently undergoing phase III clinical trials as an anticancer agent. It was noted that the desalting of protein samples was an important factor in the detection of the complex. This study demonstrated that the presence of FPP in the system was necessary for the detection of the FPT-inhibitor complex. No pentameric complex was detected in the spectrum when the experiment was carried out in the absence of the FPP. An indirect approach was also applied to confirm the noncovalent binding of SCH 66336 to FPT by the use of an off-line size exclusion chromatography followed by liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) for the detection of the inhibitor.     

A constant entropy increase model for the selection of parallel tempering ensembles

The present paper explores a simple approach to the question of parallel tempering temperature selection. We argue that to optimize the performance of parallel tempering it is reasonable to require that the increase in entropy between successive temperatures be uniform over the entire ensemble. An estimate of the system's heat capacity, obtained either from experiment, a preliminary simulation, or a suitable physical model, thus provides a means for generating the desired tempering ensemble. Applications to the two-dimensional Ising problem indicate that the resulting method is effective, simple to implement, and robust with respect to its sensitivity to the quality of the underlying heat capacity model.     

Control of the LiFePO4 electrochemical properties using low-cost iron precursor in a melt process

Journal of Solid State Electrochemistry - LiFePO4 was prepared from low-cost iron ore concentrate (containing 4.48 wt.% SiO2 and MgO, CaO and Al2O3 below 0.5 wt.% as contaminant)...     

Global exploration of the energy landscape of solids on the ab initio level

Predicting which crystalline modifications can be present in a chemical system requires the global exploration of its energy landscape. Due to the large computational effort involved, in the past this search for sufficiently stable minima has been performed employing a variety of empirical potentials and cost functions followed by a local optimization on the ab initio level. However, this entails the risk of overlooking important modifications that are not modeled accurately using empirical potentials. In order to overcome this critical limitation, we develop an approach to employ ab initio energy functions during the global optimization phase of the structure prediction. As an example, we perform a global exploration of the landscape of LiF on the ab initio level and show that the relevant crystalline modifications are found during the search.     

[3+2] Cycloaddition-mediated synthesis of 3-methylsulfanyl-pyrrolidine-3-carboxylic acid methyl ester

1,3-Dipolar cycloaddition reactions are fundamental processes in organic chemistry. Herein we report [3+2] annulation of thiomethylacrylate 2 and azomethine ylide precursor 3 towards the synthesis of novel 3-methylsulfanyl-pyrrolidine 5. Alternatively, we have also explored the alkylation of 7 with dimethyldisulfide/LDA for the introduction of thiomethyl group towards the synthesis of 5 in moderate to good yields. Efficacy of these two routes under various conditions/catalysts for the synthesis of 5 is presented.     

Ignition of a sequential combustor: Evidence of flame propagation in the autoignitable mixture

Ignition of the second stage in a lab-scale sequential combustor is investigated experimentally. A fuel mixing section between jet-in-cross-flow injection and the second stage chamber allows the fuel and vitiated, hot cross-flow to partially mix upstream of the main heat release zone. The focus of the present work is on the transient ignition process leading to a stable flame in the second stage. High-speed OH-PLIF as well as OH chemiluminescence imaging is applied to obtain complementary planar and line-of-sight integrated information on the ignition. We find experimental evidence for the co-existence of two regimes dominating the chamber ignition, i.e. autoignition and flame propagation. As the mass flow of the dilution air injected downstream of the first stage is increased (i.e. mixing temperatures in the fuel mixing section are decreased), we transition from an autoignition to a flame propagation dominated regime. Hysteresis in the ignition behavior is observed indicating that the first stage in a sequential combustor may be operated at leaner conditions than required for ignition of the second stage. The time traces of integral heat release obtained simultaneously with a photomultiplier tube show distinct features depending on the dominating regime, which is important for high-pressure testing with limited optical access.     

Evidence for itineracy in the anticipated Kondo insulator FeSi: a quantitative determination of the band renormalization

A comparison of high-resolution, angle-resolved photoemission spectroscopy (ARPES) data with ab initio band-structure calculations by density functional theory for the anticipated Kondo insulator FeSi shows that the experimental dispersions can quantitatively be described by an itinerant behavior provided that an appropriate self-energy correction is included, whose real part describes the band renormalization due to interactions of the Fe 3d electrons. The imaginary part of the self-energy, on the other hand, determines the linewidth of the quasiparticle peaks in the ARPES data. We use a model self-energy which consistently describes both the renormalized single-particle dispersion and the energy-dependent linewidth of the Fe 3d bands. These results are clear evidence that FeSi is an itinerant semiconductor whose properties can be explained without a local Kondo-like interaction.     

Direct Observation of the Electroadsorptive Effect on Ultrathin Films for Microsensor and Catalytic‐Surface Control

Microchemical sensors and catalytic reactors make use of gases during adsorption in specific ways on selected materials. Fine‐tuning is normally achieved by morphological control and material doping. The latter relates surface properties to the electronic structure of the bulk, and this suggests the possibility of electronic control. Although unusual for catalytic surfaces, such phenomena are sometimes reported for microsensors, but with little understanding of the underlying mechanisms. Herein, direct observation of the electroadsorptive effect by a combination of X‐ray photoelectron spectroscopy and conductivity analysis on nanometre‐thick semiconductor films on buried control electrodes is reported. For the SnO₂/NO₂ model system, NO₃ surface species, which normally decay at the latest within minutes, can be kept stable for 1.5 h with a high coverage of 15 % under appropriate electric fields. This includes uncharged states, too, and implies that nanoelectronic structures provide control over the predominant adsorbate conformation on exterior surfaces and thus opens the field for chemically reactive interfaces with in situ tunability.