Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess

Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2/(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and ¹H nuclear magnetic resonance (¹H-NMR) methods. Chiral configurations could also be differentiated using CD or ¹H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10⁻⁶ mol·L⁻¹). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers.     

Ambient Technology — Now You See It, Now You Don't

The continuing progression of Moore's Law has enabled the miniaturisation and dramatic cost reduction in electronics over the last ten years. For a truly pervasive communications environment the challenges of hiding key hardware technologies from the user are rapidly being overcome. This paper reviews the status of these hardware technology developments in the pervasive space and briefly discusses other contributing factors that will enable the pervasive vision to be realised.     

Efficient diode-pumped single-frequency erbium:ytterbium fiberlaser

We report a 7.6-mW single-frequency fiber laser operating at 1545 nm, using for the first time an Er³⁺:Yb³⁺ doped fiber and a fiber grating output coupler. The laser did not exhibit self-pulsation, which is a typical problem in short three-level fiber lasers, and had a relative intensity noise (RIN) level below -145.5 dB/Hz at frequencies above 10 MHz. The linewidth of the laser was limited by the relaxation oscillation sidebands in the optical spectrum and was typically less than 1 MHz     

Optical networks for local loop applications

Some of the options for optical technology within the local loop environment are examined. In particular, passive shared access networks have been considered in some detail. These networks show great promise for delivering existing telephone services to small to medium business customers (4-30 lines) economically by the early 1990s. Extending fiber to the home will also be possible by virtue of a similar passive network infrastructure for customers requiring new broadband services beyond the single telephone line. For one-line plain old telephone service (POTS) customers, an intermediate approach of terminating the fiber network at the final network distribution point, with copper retained for the final leg, may be used prior to the provision of broadband services. A key feature of the passive optical network architecture is the use of wavelength-division multiplexing (WDM) as an upgrade strategy, allowing graceful upgrading from telephone services to multichannel high-definition television (HDTV) on gigabit/second bearers and full two-way switched broadband services employing wavelength routing across the network     

A stereoselective cobalt-containing nitrile hydratase

Nitrile hydratase from Pseudomonas putida NRRL-18668 has been purified and characterized. The purified enzyme catalyzes the hydration of 2(S)-(4'-chlorophenyl)-3-methylbutyronitrile at least fifty times faster than that of 2(R)-(4'-chlorophenyl)-3-methylbutyronitrile. This enzyme is a member of the class of nitrile hydratase that contains cobalt. Visible absorption and CD spectra suggest the cobalt exists as a non-corrin low-spin Co3+ ion in a tetragonally-distorted octahedral ligand field. Chemical reduction of the native enzyme results in a species with the EPR signature of a low-spin Co2+ complex. Like the other cobalt-containing nitrile hydratases, this enzyme is relatively stable, maintaining its activity below 35 degrees C, and it shows a broad activity optimum between pH 7.2 and 7.8. The structural genes for this enzyme have been cloned and sequenced. The deduced amino acid sequences for the alpha and beta subunits show 48-63% and 35-41% homology, respectively, to other sequenced nitrile hydratases. In particular, the cysteine residues in the alpha subunit that have been suggested to coordinate the metal ion in the iron-containing nitrile hydratases [Brennan, B. A., Cummings, J. G., Chase, D. B., Turner, I. M., Jr., & Nelson, M. J. (1996) Biochemistry 35, 10068-10077] are conserved in this enzyme, suggesting that this nitrile hydratase, like the enzyme from Rhodococcus rhodochrous J1, is a member of a newly described class of metalloenzymes with Co3+-thiolate ligation [Brennan, B. A., Alms, G., Nelson, M. J., Durney, L. T., & Scarrow, R. C. (1996) J. Am. Chem. Soc. 118, 9194-9195].