Chelating and Tellurolate Ligand‐Transfer Studies of the Complex fac‐[Fe(CO)3(TePh)3]−: Crystal Structures of Heterodinuclear (CO)3Mn(μ‐TePh)3Fe(CO)3 and CpNi(TePh)(PPh3)

Complex fac‐[Fe(CO)₃(TePh)₃]^? was employed as a “metallo chelating” ligand to synthesize the neutral (CO)₃Mn(μ‐TePh)₃Fe(CO)₃ obtained in a one‐step synthesis by treating fac‐[Fe(CO)₃(TePh)₃]^? with fac‐[Mn‐(CO)₃(CH₃CN)₃]⁺. It seems reasonable to conclude that the d⁶ Fe(II) [(CO)₃Fe(TePh)₃]^? fragment is isolobal with the d⁶ Mn(I) [(CO)₃Mn(TePh)₃]^2? fragment in complex (CO)₃Mn(μ‐TePh)₃Fe(CO)₃. Addition of fac‐[Fe(CO)₃(TePh)₃]^? to the CpNi(I)(PPh₃) in THF resulted in formation of the neutral CpNi(TePh)(PPh₃) also obtained from reaction of CpNi(I)(PPh₃) and [Na][TePh] in MeOH. This investigation shows that fac‐[Fe(CO)₃(TePh)₃]^? serves as a tridentate metallo ligand and tellurolate ligand‐transfer reagent. The study also indicated that the fac‐[Fe(CO)₃(SePh)₃]^? may serve as a better tridentate metallo ligand and chalcogenolate ligand‐transfer reagent than fac‐[Fe(CO)₃(TePh)₃]^? in the syntheses of heterometallic chalcogenolate complexes.     

Analysis of Petroleum Distillates from Fire Debris Using Supercritical Fluid Extraction with a Two‐Level Orthogonal Array Experimental Design

A supercritical fluid extraction (SFE) method was developed in the present study as an effective sample pretreatment technique of petroleum distillates from fire debris. Three petroleum distillates were used as target analytes, including 95 unleaded gasoline, kerosene, and premium diesel. An orthogonal array (L16) experimental design was adopted to separately evaluate primary SFE experimental factors. The SFE efficiencies of petroleum distillates at various extraction conditions were examined and the optimized SFE conditions were identified. Experimental results demonstrated that the optimized SFE method not only provided an effective extraction method for the spiked sample, but also successfully recovered residues of petroleum distillates from fire debris.     

Brownian dynamics simulations with stiff finitely extensible nonlinear elastic-Fraenkel springs as approximations to rods in bead-rod models

A very stiff finitely extensible nonlinear elastic (FENE)-Fraenkel spring is proposed to replace the rigid rod in the bead-rod model. This allows the adoption of a fast predictor-corrector method so that large time steps can be taken in Brownian dynamics (BD) simulations without over- or understretching the stiff springs. In contrast to the simple bead-rod model, BD simulations with beads and FENE-Fraenkel (FF) springs yield a random-walk configuration at equilibrium. We compare the simulation results of the free-draining bead-FF-spring model with those for the bead-rod model in relaxation, start-up of uniaxial extensional, and simple shear flows, and find that both methods generate nearly identical results. The computational cost per time step for a free-draining BD simulation with the proposed bead-FF-spring model is about twice as high as the traditional bead-rod model with the midpoint algorithm of Liu [J. Chem. Phys. 90, 5826 (1989)]. Nevertheless, computations with the bead-FF-spring model are as efficient as those with the bead-rod model in extensional flow because the former allows larger time steps. Moreover, the Brownian contribution to the stress for the bead-FF-spring model is isotropic and therefore simplifies the calculation of the polymer stresses. In addition, hydrodynamic interaction can more easily be incorporated into the bead-FF-spring model than into the bead-rod model since the metric force arising from the non-Cartesian coordinates used in bead-rod simulations is absent from bead-spring simulations. Finally, with our newly developed bead-FF-spring model, existing computer codes for the bead-spring models can trivially be converted to ones for effective bead-rod simulations merely by replacing the usual FENE or Cohen spring law with a FENE-Fraenkel law, and this convertibility provides a very convenient way to perform multiscale BD simulations.     

Stage-frit: A straightforward sub-2 μm nano-liquid chromatography column fabrication for proteomic analysis

In this work we demonstrated a facile method for the fabrication of C18 coordination polymer gel in a capillary, called stage-frit, which was efficiently applied to pack sub-2 μm C18 beads into the capillary by a high pressure bomb for the online separation of proteolytic peptides. The back pressure of the column with 10 cm × 75 μm i.d. is regularly lower than 170 bar at a flow rate of 300 nl/min, which could be operated on a common nanoLC system instead of nanoUPLC system due to the good permeability, low back pressure and high mechanical stress of the frit that will totally reduce the cost for the purchase of instrument. The stage-frit allows long-term continuous flow of the solvent and no significant beads loss or pressure instability was observed during the period. The repeatability of retention time for fifteen BSA tryptic peaks was found to be less than 1.08% (RSD) in six time nanoLC-ESI-MS/MS experiments. The average full width at half maximum (FWHM) of peptide peaks is 5.87 s. The sub-2 μm stage-frit nanoLC column showed better sensitivity than the commercial available for large scale proteomic analysis of total tissue proteins from human spleen. The number of identified peptides is approximately 0.4-fold and 0.2-fold higher than that obtained by utilizing commercial columns packed with 3 μm and 1.8 μm C18 materials, respectively. In the field of analytical chemistry, particularly the use of nanoLC systems, stage-frit nanoLC column offers a great potential for the separation of complex mixtures.     

Dibromomethane as one-carbon source in organic synthesis: total synthesis of (±)-canadensolide

A diastereoselective total synthesis of (±)-canadensolide is described. The key step is to introduce the α-methylene group by the ozonolysis of mono-substituted alkenes followed by reaction with a preheated mixture of CH₂Br₂-Et₂NH.     

Hepatobiliary excretion and brain distribution of caffeine in rats using microdialysis

To investigate the pharmacokinetic mechanism of hepatobiliary excretion and brain distribution of caffeine, this study uses a method based on microdialysis technique and liquid chromatography that allows continuous and concurrent in vivo monitoring of extracellular caffeine in the blood, brain and bile of anesthetized rats following the administration of caffeine (3 or 10 mg/kg, i.v.) through the femoral vein. Dialysates of the blood, brain and bile were directly injected onto the liquid chromatographic system and no further clean-up procedures were required. The study design consisted of two groups of six rats in parallel: the rats of the control group received caffeine (3 or 10 mg/kg, i.v.) alone and those of the cyclosporine treated-group were injected cyclosporine (10 mg/kg, i.v.) 10 min prior to caffeine administration (3 or 10 mg/kg, i.v.). The decline of caffeine in the blood, brain striatum and bile suggested that caffeine had rapid exchange and equilibration between the peripheral compartment and the central nervous system. In addition, the results indicated that caffeine underwent hepatobiliary excretion and was distributed into brain. When cyclosporine was co-administered, the pharmacokinetic parameters were not significantly altered. The results of this study reveal that the pharmacokinetic mechanism of hepatobiliary excretion and brain distribution of caffeine might not relate to P-glycoprotein.     

Miniaturized Sequencing Gel System for Quick Analysis of DNA by Hydroxyl Radical Cleavage

We described a simple and quick miniaturized sequencing gel system for DNA analysis. Two major modifications were made to the previously reported miniaturized DNA sequencing gel system to achieve high-resolution hydroxyl radical cleavage analysis: including formamide in the miniaturized gel and providing uniform heating during electrophoresis. Our method enables one to reduce the cost for chemicals and to significantly reduce electrophoresis time. Furthermore, minimal gel handling simplifies the entire process. We show that the resolution of DNA fragments obtained by hydroxyl radical cleavage for the miniaturized gel is similar to that of a large conventional sequencing gel.     

Controlled release properties of Chitosan encapsulated volatile Citronella Oil microcapsules by thermal treatments

This research uses modified orifice method to prepare the O/W type Chitosan encapsulated volatile Citronella Oil microcapsules. In this article, we investigated the forming condition of microcapsules and the influence to sustained release effect of volatile Citronella Oil by applying thermal pretreatment to microcapsules. The results suggest that the forming of microcapsules should be processed under the fundamental conditions of: (1) the concentration of Chitosan is at least 0.2 wt%, (2) NaOH is greater than 0.1 wt%, and (3) with the additive of coconut oil as natural surfactant, so that we could obtain final product of microcapsules with better formation and dispersion. The changes in concentration of Chitosan will affect the encapsulation efficiency of the volatile Citronella Oil. When the concentrations of Chitosan are 0.5%, 1.0% and 1.5%, the encapsulation efficiencies are 98.2%, 95.8% and 94.7%, respectively. The particle size of Chitosan microcapsules would decrease as the emulsification stirring speed increases. When the stirring speeds are 400 rpm, 800 rpm, and 1500 rpm, the average particle sizes of microcapsules produced are 225 ± 24 μm, 131 ± 20 μm, and 11 ± 3 μm, respectively. If the microcapsules were thermal pretreated at 80 °C, the structure of Chitosan wall membrane would shrink and thus achieve the effect of sustained release. The sustaining effect would increase along with treatment time increases.     

Study on tribological behaviors of short glass fiber and polytetrafluoroethylene reinforced polycarbonate composites via a d‐optimal mixture design

This study analyzed variations of tribological behaviors that depend on the injection molding techniques during the blending of short glass fiber (SGF) and polytetrafluoroethylene (PTFE) reinforced polycarbonate (PC) composites. The proposed planning of blending experiments is to use a D‐optimal mixture design (DMD). The tribological behaviors of friction coefficient and wear mass loss were selected for discussion. Nine experimental runs, based on a DMD method, utilized to train the back‐propagation neural network (BPNN) and then the simulated annealing algorithm (SAA) approach is applied to search for an optimal mixture ratio setting. In addition, the result of BPNN integrating SAA was also compared with response surface methodology (RSM) approach. The results of confirmation experiment show that DMD, RSM, and BPNN integrating SAA method are effective tools for the optimization of reinforced process. Furthermore, the scanning electron microscope (SEM) images show that the abundant debris are peeled off from the matrix materials and predominant delamination mechanisms and plastic deformation are shown on the worn surface after tribological behavior tests. Copyright © 2010 John Wiley & Sons, Ltd.