Relative spatial profiles of barium ion and atom in the argon inductively coupled plasma as obtained by laser excited fluorescence

Relative ionic and atomic fluorescence profiles for barium have been obtained in an argon inductively coupled plasma by exciting different transitions with a nitrogen-laser pumped tunable dye laser and measuring the resulting fluorescence pulses with a boxcar averager. Spatially resolved profiles are directly obtained without the need of an Abel inversion procedure, with a volume resolution of approximately 0.2 mm³. The profiles are given along the excitation axis as well as along the observation axis, for different heights above the coil and different input powers. At low heights, the ion profile resembles a hollow pencil with a typical double-peaked, asymmetric distribution, while the atom profile seems to be complementary to the ion profile. Some scatter from water is also evident at low heights.     

Hindered rotation about the amido N?C bond and the tautomeric equilibrium in N,N-dimethylacetoacetamide

The molecule N,N-dimethylacetoacetamide, which is subject to a keto–enol equilibrium process in solution, also exhibits hindered rotation about the amido N? C bond. The hindered rotation rates have been studied by lineshape fit methods of the nuclear magnetic resonance spectra. In spite of some overlap of the keto and enol N-methyl proton signals, the simultaneous measurement of the two distinct energy barriers in the two forms is possible as well as a determination of the keto–enol equilibrium. The differences in free energy of activation between keto and enol forms for the rotation barrier can be related to the conjugation energy of the N? C π system with the enolic hydrogen bonded ring. Appeal to the model compound acetylacetone reveals a consistent set of energies for the keto and enol forms in the ground and transition states for internal rotation. The opportunity has been taken to reexamine and compare the keto–enol system ethylacetoacetate. Long range, solvent, concentration and temperature sensitive scalar couplings ⁴J(HH) between the enolic –OH and the adjacent methyl group in acetoacetic ester have not hitherto been reported.     

Stereoselective synthesis of 2-dienyl-substituted piperidines using an eta4-dienetricarbonyliron complex as the stereocontrolling element in a double reductive amination cascade

In the presence of NaBH(OAc)(3), a 1,5-keto-aldehyde, contained within a side-chain of an eta(4)-dienetricarbonyliron complex, undergoes a double reductive amination sequence with a series of primary amines, to provide the corresponding piperidine products in good to excellent yield. The dienetricarbonyliron complex functions as a powerful chiral auxiliary in this cascade process, exerting complete control over the stereoselectivity of the reaction, with the formation of a single diastereoisomeric product. The sense of stereoinduction has been confirmed by X-ray crystallography. Removal of the tricarbonyliron moiety can be effected with CuCl(2) to afford the corresponding 2-dienyl-substituted piperidine in excellent yield. Attempted extension of this cyclisation strategy to the corresponding azepane ring system using a 1,6-keto-aldehyde as the cyclisation precursor was unsuccessful; in this case, the reaction stopped after a single reductive amination on the aldehyde to provide an acyclic keto-amine product.     

A sensitive semi-micro column HPLC method with peroxyoxalate chemiluminescence detection and column switching for determination of MDMA-related compounds in hair

A sensitive semi-micro column HPLC method with peroxyoxalate chemiluminescence (POCL) detection and column switching has been developed for simultaneous determination of 3,4-methylenedioxymethamphetamine (MDMA) and related compounds, for example 3,4-methylenedioxyamphetamine, methamphetamine, and amphetamine, in hair. After digestion of the hair with 1 mol L⁻¹ sodium hydroxide the compounds were extracted with n-heptane and derivatized with 4-(N,N-dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole. A mixture of hydrogen peroxide and bis(2,4,5-trichloro-6-carbopentoxyphenyl)oxalate in acetonitrile was used as post-column CL reagent. Calibration plots showed linearity was good (r = 0.999); detection limits were 0.02–0.16 ng mg⁻¹ hair at a signal-to-noise ratio of 3. The precision of the method, as RSD (n = 5), in intra-day and inter-day assays was better than 5.0 and 6.9%, respectively. The proposed method was sufficiently sensitive to detect low ng mg⁻¹ levels of MDMA and related compounds in hair, and could be used for quantification of the compounds in hair samples from patients treated in a chemical dependency unit.     

The time required to focus on a cued signal frequency

How quickly can a listener focus on a single tonal cue that indicates the frequency of an upcoming signal? Initial measurements were made with frequency uncertainty (signal frequency varies randomly from trial to trial) and with certainty (same frequency on all trials). Measured by a yes-no procedure, thresholds for 40- and 20-ms signals presented in continuous broadband noise at 50 dB SPL were higher in uncertainty than in certainty; the difference decreased monotonically from 5 dB at frequencies below 500 Hz to under 3 dB above about 2500 Hz. This decrease in the detrimental effect from uncertainty, which comes about with increasing signal frequency, may result from preferential attention to higher frequencies. In a second experiment, frequency again varied randomly, but each trial now began with a cue at the signal frequency. The critical variable was the delay from cue onset to signal onset. A delay of 352 ms eliminated the detrimental effect of frequency uncertainty at all frequencies. At the shortest delays of 52 and 82 ms the detrimental effect was reduced primarily at lower frequencies. Our analysis suggests that shifting focus to a cued frequency region, under optimal stimulus conditions, requires less than 52 ms.     

Palladium catalyzed alkoxy- and aminocarbonylation of vinyl tosylates

The palladium catalyzed alkoxycarbonylation and aminocarbonylation of vinyl tosylates are described. A variety of ketone and aldehyde derived vinyl tosylates may be carbonylated in the presence of primary, secondary, and tertiary alcohols, or primary and secondary amines, to provide the corresponding esters and amides in good yields. The alkoxycarbonylation was applied to a short synthesis of isoguvacine.     

Chelation controlled reductive amination of cyclic ketones to trans-4-methoxycyclohexylamines: 9-BBN reduction mediated with FeCl3

A novel trans-diastereoselective reductive amination of 4-substituted cyclohexanones is described using 9-BBN as reducing agent in the presence of FeCl₃. The method permits efficient synthesis of structurally diverse 4-trans-alkoxycyclohexylamines.     

The Influence of Silkworm Species on Cellular Interactions with Novel PVA/Silk Sericin Hydrogels

Sericin peptides and PVA are chemically modified with methacrylate groups to produce a covalent PVA/sericin hydrogel. Preservation of the sericin bioactivity following methacrylation is confirmed, and PVA/sericin hydrogels are fabricated for both B. mori and A. mylitta sericin. Cell adhesion studies confirm the preservation of sericin bioactivity post incorporation in PVA gels. PVA/A. mylitta gels are observed to facilitate cell adhesion to a significantly greater degree than PVA/B. mori gels. Overall, the incorporation of sericin does not alter the physical properties of the PVA hydrogels but does result in significantly improved cellular interaction, particularly from A. mylitta gels.

     

On iterative techniques for computing flow in large two-dimensional discrete fracture networks

Computation of flow in discrete fracture networks often involves solving for hydraulic head values at all intersection points of a large number of stochastically generated fractures inside a bounded domain. For large systems, this approach leads to the generation of problems involving highly sparse matrices which must be solved iteratively. Distributions of fracture lengths spanning over several orders of magnitude, and the randomness of fracture orientations and locations, lead to coefficient matrices that are devoid of any regular structure in the sparsity pattern. In addition to the rapid increase in computational effort with increase in the size of the fracture network, the spread in the distribution of fracture parameters, such as length and transmissivity, dramatically influences the convergence behavior of the system of linear equations. An overview of the discrete fracture network (DFN) methodology for computation of flow is presented along with a comparative study of various Krylov subspace iterative methods for the resulting class of sparse matrices. The rate of convergence of the iterative techniques is found to exhibit a systematic pattern with respect to changes in statistical parameters of the stochastically generated fracture networks. Salient features of the observed trends in the convergence pattern are discussed and guidelines for design of DFN algorithms are provided.