Mode-locked fiber laser frequency-controlled with an intracavity electro-optic modulator

We demonstrate a mode-locked, erbium-doped fiber laser with its repetition frequency synchronized to a second fiber laser via an intracavity electro-optic modulator (EOM). With servo control from the EOM (bandwidth approximately 230 kHz) and a slower speed intracavity piezoelectric transducer (resonance at approximately 20 kHz), we demonstrate stabilization of the repetition frequency with an in-loop rms timing jitter of 10 fs, integrated over a bandwidth from 1 Hz to 100 kHz. This represents what is to our knowledge the first time an EOM has been introduced inside a mode-locked laser cavity for fast servo action and the lowest timing jitter reported for a mode-locked fiber laser.     

A structural and n.m.r. investigation of chlorodinitrosyl bis(triphenyl phosphine) osmium(1+) tetrafluoroborate, [OsCl(NO)2(PPh3)2]BF4

Summary [OsCl(NO)₂(PPh₃)₂]BF₄ has been synthesised from [OsCl(CO)(NO)(PPh₃)₂] and NOBF₄ and characterised in the solid state by a single crystal x-ray analysis determination and in solution by³¹P{¹H} and¹⁵N n.m.r. studies. The nitrosyl ligands in [OsCl(NO)₂(PPh₃)₂]⁺ are approximately linear, and 170(1)⁰, and the co-ordination geometry about the metal ion is close to trigonal bipyramidal. This contrasts with the occurrence of a linear and a bent nitrosyl ligand in [RuCl(NO)₂(PPh₃)₂]⁺ and a square-pyramidal metal geometry. In solution the¹⁵N n.m.r. spectrum of a 50%¹⁵N enriched sample of [OsCl(NO)₂(PPh₃)₂]⁺ shows an equilibrium isotope effect similar to that reported for [RuCl(NO)₂(PPh₃)₂]⁺ and suggests that both complexes exist in solution as rapidly equilibrating isomeric forms.     

Development of a trace gas stable isotope capture system in a mobile laboratory for temporal and spatial sampling of field and laboratory experiments

We describe the development of a novel mobile field laboratory, purposely designed for the automated capture and subsequent stable isotopic analyses of multiple gas samples. The multiple capture system is integrated into a mobile laboratory that is fully capable of measuring the concentration of carbon dioxide, methane and nitrous oxide trace gases in a flow-through system connected to a gas chromatograph fitted with both electron capture and flame ionisation detectors. The capture of gases is achieved by routing samples through a series of 135 mL gas flasks that are sealed by micro-solenoid valves triggered by a timing system. Trace gas light stable isotope ratio mass spectrometry can then be carried out on gas samples collected by the system (NERC (15)N Stable Isotope Facility). The excitingly unique potential of the system to the ecological research field is that it will allow the collection of cyclical data for three different trace gases both in real-time and in situ. We present data arising from the validation of this mobile system as well as a preliminary experimental assessment of this technique. This technique was used to measure delta(13)C in CO(2) and CH(4) in soil gases released from waterlogged cores and delta(13)C-CH(4) values were significantly depleted in wet cores compared with dry ones (p < 0.001).     

Redox modulation of benzene triimides and diimides via noncovalent interactions

[reaction: see text] Mellitic triimides undergo three sequential one-electron reduction processes whose potentials are significantly lowered in the presence of alkyl thioureas. The two sequential reductions of benzene diimides are similarly stabilized. Calculation of the relative free energy change between the different electronic states of the imide acceptors and their corresponding alkyl thiourea complexes indicates dramatic increases in hydrogen bond strength with increasing acceptor charge density.     

Evaluation and validation of the ABI 3700, ABI 3100, and the MegaBACE 1000 capillary array electrophoresis instruments for use with short tandem repeat microsatellite typing in a forensic environment

The demand for high-throughput DNA profiling has increased with the introduction of national DNA databases and has led to the development of automated methods of short tandem repeat (STR) profile production; however, a potential bottleneck still exists at the gel electrophoresis stage. Capillary electrophoresis sequencers capable of processing 96 samples with considerably reduced manual intervention are now available. In this paper, we compare the ABI Prism 377 slab-gel sequencer currently used by the Forensic Science Service with three leading capillary array electrophoresis instruments: the ABI Prism 3700, the Amersham MegaBACE 1000 and the 16-capillary ABI Prism 3100. We describe the experiments used to evaluate and validate these platforms for forensic use with the STR multiplex Ampf/STR SGMplus [1, 2], along with comparative data from the ABI Prism 377 sequencer.     

Effect of molecular oxygen on the variable-temperature 29Si MAS NMR spectra of zeolite-sorbate complexes

Structure determinations of siliceous zeolite-sorbate host-guest complexes by solid-state NMR require highly resolved 29Si MAS NMR spectra. As the temperature is lowered, the 29Si MAS NMR spectra of many zeolite-sorbate complexes become broadened such that the resolution of the individual 29Si peaks is lost, limiting the application of solid-state NMR for structure determination. It is shown that the 29Si peak widths are related to the 29Si T2 relaxation times and that the source of the 29Si relaxation and the line broadening is paramagnetic molecular oxygen in the channels of the zeolite. Removal of the oxygen by purging the sample with nitrogen gas leads to a dramatic increase in the resolution of the 29Si MAS NMR spectrum of the p-dibromobenzene/ZSM-5 complex. An analysis of the individual 29Si T1 relaxation times reveals that the oxygen molecules are localized mainly in the zigzag channels of ZSM-5, suggesting that the p-dibromobenzene molecules are located in the channel intersections.     

Surface enhanced Raman spectroscopy (SERS) for the discrimination of Arthrobacter strains based on variations in cell surface composition

Surface enhanced Raman spectroscopy (SERS) is a rapid and highly sensitive spectroscopic technique that has the potential to measure chemical changes in bacterial cell surface in response to environmental changes. The objective of this study was to determine whether SERS had sufficient resolution to differentiate closely related bacteria within a genus grown on solid and liquid medium, and a single Arthrobacter strain grown in multiple chromate concentrations. Fourteen closely related Arthrobacter strains, based on their 16S rRNA gene sequences, were used in this study. After performing principal component analysis in conjunction with Linear Discriminant Analysis, we used a novel, adapted cross-validation method, which more faithfully models the classification of spectra. All fourteen strains could be classified with up to 97% accuracy. The hierarchical trees comparing SERS spectra from the liquid and solid media datasets were different. Additionally, hierarchical trees created from the Raman data were different from those obtained using 16S rRNA gene sequences (a phylogenetic measure). A single bacterial strain grown on solid media culture with three different chromate levels also showed significant spectral distinction at discrete points identified by the new Elastic Net regularized regression method demonstrating the ability of SERS to detect environmentally induced changes in cell surface composition. This study demonstrates that SERS is effective in distinguishing between a large number of very closely related Arthrobacter strains and could be a valuable tool for rapid monitoring and characterization of phenotypic variations in a single population in response to environmental conditions.     

Alkali base-initiated Michael addition/alkyne carbocyclization cascades

A new cascade reaction involving an intramolecular Michael addition followed by an alkyne carbocyclization is presented. The reaction is promoted by a substoichiometric amount of KHMDS and represents one of the rare examples where the carbocyclization of an unactivated alkyne is mediated by an alkali metal base, under mild conditions. The reaction allows the generation of functionally dense, stereochemically defined, tricyclic structures possessing three adjacent stereocenters in good yields and with high stereoselectivity.