Growth, new growth, and amplification of carbon nanotubes as a function of catalyst composition

Carbon nanotubes (CNTs) have been grown using Fe, Co, Ni, and Co/Fe spin-on-catalyst (SOC) systems, involving the metal salt dispersed with a spin-on-glass precursor. During initial growth runs (CH4/H2/900 degrees C), the CNT yield followed the order Co-SOC > Fe-SOC > Ni-SOC. The Fe catalysts produced the longest nanotubes at the expense of a larger average CNT diameter and broader diameter distribution than the Co-SOC system. A series of Co/Fe-SOCs were prepared where as the atomic percentage of Co is increased nucleation of CNT increases but the CNT length decreases. The linear relationship between the diameter and length of CNTs grown from the Co/Fe-SOC suggests that slow growth is beneficial with respect to control over CNT diameter. After initial CNT growth, the original samples were subjected to additional growth runs. Four individual reactions were observed in the Fe-SOC and binary Co/Fe-SOC: regrowth (amplification), double growth (a second CNT growing from a previously active catalyst), CNT etching, and nucleation from initially inactive catalysts (new growth). CNT etching was observed for the mixed catalyst systems (Co/Fe-SOC) but not for either Fe-SOC or Co-SOC. During the regrowth experiments, CNTs were observed that were not present after the initial growth run (and were not as a result of amplification or double growth). Thus, catalysts, which were initially inactive toward nucleation of CNTs in the original growth run, are capable of becoming activated when placed back into the furnace and submitted to regrowth under identical conditions.     

Two-dimensional Raman and Raman optical activity correlation analysis of the alpha-helix-to-disordered transition in poly(L-glutamic acid)

Rich and complex Raman scattering and Raman optical activity (ROA) spectra have been measured monitoring the pH induced alpha-helix-to-disordered conformational transition in poly(L-glutamic acid). Two-dimensional (2D) correlation techniques have been applied to facilitate a comprehensive analysis of these two complementary spectral sets. Synchronous contour plots have identified band assignments of alpha-helical and disordered conformations, and have revealed bands characteristic of changes in the protonation state of the polypeptide. Asynchronous plots, on the other hand, have probed the relative sequential orders of intensity changes indicating a decrease in intensity of alpha-helical bands in the backbone skeletal stretch region, followed by a subsequent decrease in intensity in the extended amide III and amide I regions, underlying the appearance of disordered structure, including poly(L-proline) II (PPII) helix. The application of a 2D correlation 'moving' window has also disclosed two distinct phases during helix unfolding in the alpha-helix-to-disordered transition, occurring at approximately pH 4.9 and approximately pH 5.2, possibly a result of the difference in helical stability between the end and central regions of the alpha-helix. This paper demonstrates the potential value of combining 2D Raman, 2D ROA and moving window correlation techniques for the detailed investigation of complex and subtle changes of secondary structure during the unfolding mechanisms of polypeptides and proteins.     

Fullerene-derivatized amino acids: synthesis, characterization, antioxidant properties, and solid-phase peptide synthesis

A series of [60]fullerene-substituted phenylalanine (Baa) and lysine derivatives have been prepared by the condensation of 1,2-(4'-oxocyclohexano)fullerene with the appropriately protected (4-amino)phenylalanine and lysine, respectively. Conversion of the imine to the corresponding amine is achieved by di-acid catalyzed hydroboration. The reduction of the imine is not accompanied by hydroboration of the fullerene cage. The [70]fullerene phenylalanine derivative has also been prepared as have the di-amino acid derivatives. The compounds were characterized by MALDI-TOF mass spectrometry, UV/Vis spectroscopy, and cyclic voltammetry. 1H and 13C NMR spectroscopy allowed the observation of diastereomers. Fullerene-substituted peptides may be synthesized on relatively large scale by solid-phase peptide synthesis. The presence of the C60-substituted amino acid in a peptide has a significant effect on the secondary structures and self-assembly properties of peptides as compared to the native peptide. The antioxidant assay of Baa and a Baa-derived anionic peptide was determined to be significantly more potent than Trolox.     

Risk bounds for model selection via penalization

Performance bounds for criteria for model selection are developed using recent theory for sieves. The model selection criteria are based on an empirical loss or contrast function with an added penalty term motivated by empirical process theory and roughly proportional to the number of parameters needed to describe the model divided by the number of observations. Most of our examples involve density or regression estimation settings and we focus on the problem of estimating the unknown density or regression function. We show that the quadratic risk of the minimum penalized empirical contrast estimator is bounded by an index of the accuracy of the sieve. This accuracy index quantifies the trade-off among the candidate models between the approximation error and parameter dimension relative to sample size. If we choose a list of models which exhibit good approximation properties with respect to different classes of smoothness, the estimator can be simultaneously minimax rate optimal in each of those classes. This is what is usually called adaptation. The type of classes of smoothness in which one gets adaptation depends heavily on the list of models. If too many models are involved in order to get accurate approximation of many wide classes of functions simultaneously, it may happen that the estimator is only approximately adaptive (typically up to a slowly varying function of the sample size). We shall provide various illustrations of our method such as penalized maximum likelihood, projection or least squares estimation. The models will involve commonly used finite dimensional expansions such as piecewise polynomials with fixed or variable knots, trigonometric polynomials, wavelets, neural nets and related nonlinear expansions defined by superposition of ridge functions. Received: 7 July 1995 / Revised version: 1 November 1997     

A three-dimensional hydrodynamic model in curvilinear co-ordinates with collocated grid

A three-dimensional hydrodynamic model has been developed for turbulent flows with free surface. In the horizontal x–y-plane, a boundary-fitted curvilinear co-ordinate system is adopted, while in the vertical direction, a σ-co-ordinate transformation is used to represent the free surface and bed topography or lower boundary. Using the finite volume method, the convection terms are discretized using Roe's second-order-accurate scheme. The governing equations are solved in a collocated grid system by a fractional three-step implicit algorithm that has been developed to handle the velocity–pressure–depth coupling problem of free surface incompressible fluid flows. The present study is the extension of previous work to three-dimensional turbulent flows. The model has been applied to three test cases. Comparison with available data shows that the model developed is successful, and is valuable to engineering application. © 1998 John Wiley & Sons, Ltd.     

Unusual Co-Crystallization of both Monomeric and Dimeric Forms of Cu[PhN(py)quin]Cl<Subscript>2</Subscript>

Abstract  

The aryl functionalized diquinolyl amine MesN(quin)₂ (1) and the pyridyl-quinolyl amine (2,6-iPr₂C₆H₃)N(py)quin (2) have been prepared via palladium catalyzed cross-coupling of substituted anilines with 2-chloroquinoline. The HBF₄ acid salts of (2,6-ⁱPr₂C₆H₃)N(quin)₂ (3) and MesN(py)quin (4), as well as the copper complex [Cu{PhN(py)quin}Cl₂] (5) have been prepared in order to probe the effect that ligand coordination has on its geometry. The molecular structures of each have been determined by X-ray crystallography. The free ligands 1 and 2 crystallize in three-bladed propellar conformations, having smaller degrees of “pitch” between the two heterocycles than either has with the aryl “blade”, allowing for greater heterocycle π-system overlap with the amine lone pair. Acid confinement of similar ligands in 3 and 4 results in forced coplanarity of the two heterocycles, which coordinate the HBF₄ proton in an asymmetric fashion. The copper complex 5 crystallizes with both monomeric and dimeric forms present in the asymmetric unit. Crystal data: (1) Space group P2₁/c, a = 14.058(3), b = 12.202(2), c = 12.831(3) ?, β = 104.61(3)°, V = 2129.8(8) ?³, Z = 4, R = 0.0596, wR₂ = 0.1453. (2) Space group P2₁/c, a = 22.250(4), b = 8.628(2), c = 23.031(5) ?, β = 92.88(3)°, V = 4370(2) ?³, Z = 8, R = 0.0514, wR₂ = 0.1323. (3) Space group Pbca, a = 13.886(3), b = 18.016(4), c = 21.347(4) ?, V = 5340(2) ?³, Z = 8, R = 0.0722, wR₂ = 0.1635. (4) Space group P2₁/c, a = 10.629(2), b = 18.489(4), c = 10.907(2) ?, β = 92.88(3), V = 2140.6(7) ?³, Z = 4, R = 0.0551, wR₂ = 0.1531. (5) Space group \text P[`1]{\text P}\bar{1}, a = 9.706(2), b = 11.325(2), c = 17.322(4) ?, α = 98.28(3), β = 94.85(3), γ = 91.83(3)°, V = 1875.6(7) ?³, Z = 1, R = 0.0481, wR₂ = 0.0946.     

Simultaneous determination of trace oxyhalides and haloacetic acids using suppressed ion chromatography-electrospray mass spectrometry

A new analytical procedure for the simultaneous determination of trace oxyhalides and haloacetic acids (HAs) in drinking water and aqueous soil extracts is described. The method uses micro-bore ion chromatography (IC) coupled with suppressed conductivity (SC) and electrospray ionization mass spectrometric detection (ESI-MS). The IC-SC-ESI-MS system included a secondary flow of 100% MeOH, which was added to the column eluate (post-suppressor) and resulted in a significant increase in sensitivity for all analytes. All ESI-MS parameters were optimized for HA analysis and sensitivity quantitatively compared to suppressed conductivity. Full analytical performance characteristics for the developed method are presented for monochloro-, monobromo-, dichloro-, dibromo-, trichloro-, bromochloro, chlorodifluoro-, trifluoro-, dichlorobromo- and dibromochloroacetic acid, as well as the oxyhalides iodate, bromate, chlorate and perchlorate. In the case of the HAs, an optimised 25-fold SPE preconcentration method meant all analytes could be readily detected well below the USEPA 60 μg/L regulatory limit using conductivity and/or ESI-MS. The IC-ESI-MS method was applied to the determination of oxyhalides and HAs in both soil extracts and drinking water samples. Soil samples were extracted using ultra pure water with subsequent determination of perchlorate at 1.68 μg/g of soil. A drinking water sample containing HAs was preconcentrated using LiChrolut EN solid phase extraction cartridges with subsequent sulphate and chloride removal. Total HAs were determined at 13 μg/L.     

781 Mbit/s photon-counting optical communications using a superconducting nanowire detector

We demonstrate 1550 nm photon-counting optical communications with a NbN-nanowire superconducting single-photon detector. Source data are encoded with a rate-1/2 forward-error correcting code and transmitted by use of 32-ary pulse-position modulation at 5 and 10 GHz slot rates. Error-free performance is obtained with -0.5 detected photon per source bit at a source data rate of 781 Mbits/s. To the best of our knowledge, this is the highest reported data rate for a photon-counting receiver.     

Helical peptoid mimics of lung surfactant protein C

Among the families of peptidomimetic foldamers under development as novel biomaterials and therapeutics, poly-N-substituted glycines (peptoids) with alpha-chiral side chains are of particular interest for their ability to adopt stable, helical secondary structure in organic and aqueous solution. Here, we show that a peptoid 22-mer with a biomimetic sequence of side chains and an amphipathic, helical secondary structure acts as an excellent mimic of surfactant protein C (SP-C), a small protein that plays an important role in surfactant replacement therapy for the treatment of neonatal respiratory distress syndrome. When integrated into a lipid film, the helical peptoid SP mimic captures the essential surface-active behaviors of the natural protein. This work provides an example of how an abiological oligomer that closely mimics both the hydrophobic/polar sequence patterning and the fold of a natural protein can also mimic its biophysical function.