Spectral features associated with nonlinear pulse compression in Bragg gratings

We report, for the first time to our knowledge, direct spectral measurements of nonlinear spectral broadening caused by nonlinear propagation through Bragg gratings written on integrated AlGaAs waveguides. The spectral broadening is associated with pulse compression from 400 to 80 ps. The high nonlinearity of AlGaAs enables high-repetition-rate, low-peak-power sources to be used, facilitating easy spectral measurements.     

Spinning Sidebands in Slow-Magic-Angle-Spinning NMR Spectra Arising from TightlyJ-Coupled Spin Pairs

Complex spinning sidebands are observed in magic-angle-spinning (MAS) NMR spectra arising from isolated tightlyJ-coupled spin pairs under slow spinning conditions. Such spinning sidebands are sensitive to the magnitude and relative orientation of the chemical-shift tensors, the dipolar-coupling tensor, and the sign of the indirect spin–spin (J) coupling. We show that it is possible to extract information concerning such NMR parameters from an analysis of the observed spinning sidebands. As an example, numerical simulations are carried out to reproduce observed³¹P MAS NMR spectra of a phosphole tetramer (1) ando-bis(diphenylphosphino)benzene (2), so that invaluable information concerning the orientations of the phosphorus chemical-shift tensors and the sign ofJ(³¹P,³¹P) can be deduced. Simulations are carried out by numerically evaluating the spin-density matrix of the spin system.     

Analysis of the Symmetry of Crystal Packing Forces by Methyl Proton Tunneling: A Strategy for the Unambiguous Assignment of the Magnetic Jahn – Teller Effect in Molecules

Intrinsic and extrinsic forces behind the distortion in metal atom clusters can be readily distinguished provided that the clusters are embedded in a suitable ligand environment and that the tunneling of the protons in the peripheral ligands is then analyzed by inelastic neutron scattering. For the [Cr₃O(OOCCH₃)₆(H₂O)₃]Cl⋅6 H₂O model system studied, the tunneling process is very sensitive to the local environment. Thus a tool is available to allow a better assessment of the cause of structural distortions.     

A Comparison of Solar Ultraviolet Radiation Exposure in Urban Canyons in Venice,Italy and Johannesburg,South Africa

Urban environments can have high-risk spaces that can provide excess personal sun exposure, such as urban or street canyons, and the spaces between buildings, among others. In these urban spaces, sun exposure can be high or low depending on several factors. Polysulphone film (PSF) was used to assess possible daily solar ultraviolet radiation (UVR) exposure in urban canyons in Venice, Italy and, for the first time in Africa, in Johannesburg, South Africa. The photodegradation of PSF upon solar exposure was monitored at a wavelength of 330 nm by ultraviolet-visible spectrophotometry, and the resultant change was converted to standard erythemal dose (SED) units (1 SED = 100 J m⁻²). Mean daily ambient solar UVR exposure measured for Venice and Johannesburg ranged between 20–28 SED and 33–43 SED, respectively. Canyon-located PSF exposures were lower in Venice (1–9 SED) than those in Johannesburg (9–39 SED), depending mainly on the sky view factor and orientation to the sun. There was large variation in solar UVR exposure levels in different urban canyons. These preliminary results should be bolstered with additional studies for a better understanding of excess personal exposure risk in urban areas, especially in Africa.     

Hydrate temperature depression of MEG solutions at concentrations up to 60 wt%. Experimental data and simulation results

Literature data for the hydrate temperature depression by mono-ethylene glycol (MEG) show some scattering and no thermodynamic model has been able to match all of the available data found in the open literature. This paper presents hydrate equilibrium data for a mixture of 88.13 mol% methane and 11.87 mol% propane with MEG added to the water phase in concentrations from 0 to 60 wt%. That particular hydrocarbon mixture was chosen because it with pure water at pressures above 60 bar shows hydrate dissociation temperatures above 20 °C and because hydrate dissociation temperatures above the freezing point of water are still seen when the aqueous phase contains 50 wt% MEG. This range of inhibitor dosage is typical in North Sea pipelines, and for optimal hydrate control it is vital to have high quality experimental data of hydrate equilibrium. Previously published data for the same hydrocarbon mixture as used in this study show a lower hydrate depression by MEG compared to other available data. The new data from this work show that MEG is more efficient as a hydrate inhibitor than the previously published data for the same system has suggested. The new data and earlier MEG inhibition data for other systems can all be modeled within experimental uncertainty using the hydrate model of Munck et al. and a conventional cubic equation of state for the H₂O-MEG component pair.     

Hydrogen and deuterium atoms in octasilsesquioxanes: experimental and computational studies

The rate of detrapping of atomic hydrogen from several octasilsesquioxanes is the same for dissolved and solid samples and is independent of the presence of other species such as free radicals or oxygen; varying the cage substituents leads to only minor differences in the activation parameters. Hydrogen atoms are found to be more strongly stabilized in homosubstituted octasilsesquioxanes compared with singly Ge-substituted cages. A kinetic isotope effect observed for the detrapping of H and D from MeT(8) is ascribed to the difference in the zero-point energies of the trapped atoms. There is a secondary H/D isotope effect in the temperature dependence of the (29)Si-superhyperfine splitting constants in the range 228-353 K. Cage relaxation has a substantial effect on the detrapping barrier but little influence on the intracage potential. Calculations using a rigid cage approximation give satisfactory agreement with zero-point parameters extracted from experimental data. Different model chemistries yield qualitatively different pictures of the dependence of the hyperfine coupling constant of the trapped H atom upon the detrapping coordinate. Within an isotropic approximation of the vibrational displacements, the B3LYP data give fairly close agreement with the experimental temperature dependence, subject to a shift of the absolute value related to known weaknesses of the method. For the Si(7)Ge cage, it is found that the transition state in which the H atom passes through a Ge-containing face is strongly favored, accounting for the larger detrapping rate parameters observed experimentally for this species.     

Novel integrated paired emitter-detector diode (PEDD) as a miniaturized photometric detector in HPLC

A novel low power, low cost, highly sensitive, miniaturized light emitting diode (LED) based flow detector has been used as optical detector for the detection of sample components in high performance liquid chromatography (HPLC). This colorimetric detector employs two LEDs, one operating in normal mode as a light source and the other is reverse biased to work as a light detector. Instead of measuring the photocurrent directly, a simple timer circuit is used to measure the time taken for the photocurrent generated by the emitter LED (lambda(max) 500 nm) to discharge the detector LED (lambda(max) 621 nm) from 5 V (logic 1) to 1.7 V (logic 0) to give digital output directly without using an A/D converter. Employing a post-column reagent method, a Nucleosil 100-7 column (functionalized with iminodiacetic acid (IDA) groups) was used to separate a mixture of transition metal complexes, manganese(II) and cobalt(II) in 4-(2-pyridylazo)-resorcinol (PAR). All optical measurements were taken by using both the in-built HPLC variable wavelength detector and the proposed paired-emitter-detector-diode (PEDD) optical detector configured in-line for data comparison. The concentration range investigated using the PEDD was found to give a linear response to the Mn(II) and Co(II) PAR complexes. The effects of flow rate and emitter LED light source intensity were investigated. Under optimised conditions the PEDD detector offered a linear range of 0.9-100 microM and LOD of 0.09 microM for Mn-PAR complex. A linear range of 0.2-100 microM and LOD of 0.09 microM for Co-PAR complex was achieved.     

Synthesis of the sedum and related alkaloids: A personal perspective

Significant recent contributions to the synthesis of the sedum alkaloids are discussed. Related compounds, such as pinidinol, porantheridine, dumetorine and the tetraponerines are also included. The syntheses are categorised according to the key motif or chemistry employed: isoxazolidines, metathesis, asymmetric aza-Michael, heterocycle lithiation, organocatalysis, aromatic heterocycles and chiral imines.     

紫外光子在星周天体化学中的作用

介于1到8个太阳质量之间的恒星在演化后期的渐近巨星分支(AGB)阶段,会以气体和尘埃的形式损失大量物质. AGB星提供了星际介质中高达35%的尘埃,其中包含形成太阳系所需要的物质. 此外,AGB星周包层是复杂有机化学所发生的重要场所之一,在其中已探测到的有机分子已超过80多个. 这里展示了AGB星自身或者其近距离的伴星所辐射的紫外光子会显著地改变星周包层的化学特性,尤其是具有团块结构的星周包层. 研究发现,在恒星存在伴星(例如白矮星)的情况下,高通量的紫外光子会破坏富碳AGB星周包层内部的H₂O分子,使其含量低于观测到的水平,并且在星周包层内部产生C⁺等物质,这与以往的星周化学模型的研究结果是不同的.