Nitrenes, diradicals, and ylides. Ring expansion and ring opening in 2-quinazolylnitrenes

Tetrazolo[1,5-a] quinazoline (9) is converted to 2-azidoquinazoline (10) on sublimation at 200 degrees C and above, and the azide-tetrazole equilibrium is governed by entropy. 2-Quinazolylnitrenes 11 and 27 and/ or their ring expansion products 14 and 29 can undergo type I (ylidic) and type II (diradicaloid) ring opening. Argon matrix photolysis of 9/10 affords 2-quinazolylnitrene (11), which has been characterized by ESR, UV, and IR spectroscopy. A minor amount of a second nitrene, formed by rearrangement or ring opening, is also observed. A diradical (19) is formed rapidly by type II ring opening and characterized by ESR spectroscopy; it decays thermally at 15 K with a half-life of ca. 47 min, in agreement with its calculated facile intersystem crossing (19T -> 19OSS) followed by facile cyclization/rearrangement to 1-cyanoindazole (21) (calculated activation barrier 1- 2 kcal/mol) and N-cyanoanthranilonitrile (22). 21 and 22 are the isolated end products of photolysis. 21 is also the end product of flash vacuum thermolysis. An excellent linear correlation between the zero-field splitting parameter D (cm(-1)) and the spin density F on the nitrene N calculated at the B3LYP/EPRIII level is reported (R-2 = 0.993 for over 100 nitrenes). Matrix photolysis of 3-phenyltetrazolo[1,5-a] quinazoline (25) affords the benzotriazacycloheptatetraene 29, which can be photochemically interconverted with the type I ring opening product 2-isocyano-alpha-diazo-alpha- phenyltoluene (33) as determined by IR and UV spectroscopy. The corresponding carbene 37, obtained by photolysis of 33, was detected by matrix ESR spectroscopy.

Single- and dual-wavelength switchable erbium-doped fiber ring laser based on intracavity polarization selective tilted fiber gratings

We propose and demonstrate a single- and dual-wavelength switchable erbium-doped fiber laser (EDFL) by utilizing intracavity polarization selective filters based on tilted fiber gratings (TFGs). In the cavity, one 45° TFG functions as an in-fiber polarizer and the other 77° TFG is used as a fiber polarization dependent loss (PDL) filter. The combined polarization effect from these two TFGs enables the laser to switch between the single- and the dual-wavelength operation with a single-polarization state at room temperature. The laser output at each wavelength shows an optical signal-to-noise ratio (OSNR) of >60 dB, a side mode suppression ratio (SMSR) of >50 dB, and a polarization extinction ratio of ~35 dB. The proposed EDFL can give stable output under laboratory conditions.

Novel imprinted polymers as artificial enzymes

Derivatives of L-histidine were investigated as suitable models for the Asp-His couple found in the catalytic triad of serine proteases. A combination of molecular dynamics and IH NMR spectroscopy suggested that the most populous conformations of N-acetyl-L-histidine and the N-acetyl-L-histidine anion were predominated by those in which the carboxylate group was gauche to the imidazole ring overcoming steric and electrostatic repulsion, suggesting there is an interaction between the carboxylate group and the imidazole ring. Kinetic studies, using imidazole, N-acetyl-L-histidine and the N-acetyl-L-histidine anion showed that in a DMSO/H20 9: 1 v/v solution, the N-acetyl-L-histidine anion catalysed the hydrolysis of p-nitrophenyl acetate at a greater rate than using either imidazole or N-acetyl-L-histidine as catalyst. This indicates that the carboxylate group affects the nucleophilicity of the unprotonated imidazole ring. 31P MAS NMR spectroscopy was investigated as a new technique for the study of the template molecule environment within the polymer networks. It was found that it was possible to distinguish between template associated with the polymer and that which was precipitated onto the surface, though it was not possible to distinguish between polymer within imprinted cavities and that which was not. Attempts to study the effect of the carboxylate group/imidazole ring interaction in the imprinted cavity of a molecularly imprinted polymer network were hindered by the method used to follow the reaction. It was found though that in a pH 8.0 buffered solution the presence of imprinted cavities increased the rate of reaction for those polymers derived from L-histidine. Some preliminary investigations into the design and synthesis of an MIP which would catalyse the oxy-Cope rearrangement were carried out but the results were inconclusive.

Refractometer based on fiber Bragg grating Fabry-Pérot cavity embedded with a narrow microchannel

We report on inscription of microchannels of different widths in optical fiber using femtosecond (fs) laser inscription assisted chemical etching and the narrowest channel has been created with a width down to only 1.2µm. Microchannels with 5µm and 35µm widths were fabricated together with Fabry-Pérot (FP) cavities formed by UV laser written fiber Bragg gratings (FBGs), creating high function and linear response refractometers. The device with a 5µm microchannel has exhibited a refractive index (RI) detection range up to 1.7, significantly higher than all fiber grating RI sensors. In addition, the microchannel FBG FP structures have been theoretically simulated showing excellent agreement with experimental measured characteristics.

Repetition-rate multiplication using a single all-pass optical cavity

We demonstrate a simple lossless method for the implementation of repetition-rate multiplication of a periodic pulse train. As it is showed, a single all-pass optical cavity (APOC) can increase the repetition rate of the output pulse train by factors of 2, 3, and 4. Two different APOC implementations, based on a Gires-Tournois interferometer and an all-pass ring resonator, are proposed and numerically demonstrated.

Multi-wavelength switchable fibre ring laser based on polarisation selective tilted fibre gratings capable of strain and temperature sensing

Using three fibre gratings with excessively tilted structures in the cavity, we have experimentally demonstrated a multiwavelength switchable erbium-doped fibre ring laser system. The three tilted gratings act as in-fibre polariser and polarisation dependent loss filters to induce the polarisation hole burning effect in the cavity for the operation of the laser at single, double, triple and quadruple wavelengths. The laser system has demonstrated good stability under room temperature conditions and also achieved a high degree of polarization (~30dB), high optical signal to noise ratio (up to 63dB) and high side mode suppression (~50dB). The system has also been investigated for temperature and strain sensing by subjecting the seeding fibre Bragg gratings (FBG) to temperature and strain variations. Since the loss band of the polarisation dependent loss filter is broader than the bandwidth of the seeding FBG, the laser output shifts in wavelength with the applied temperature and strain. The fibre ring laser has shown good responses to the temperature and strain, providing sensitivities of approximately 11.7 pm/°C and 0.85pm/µe respectively.

Identification and relative quantification of tyrosine nitration in a model peptide using two-dimensional infrared spectroscopy

Nitration of tyrosine in proteins and peptides is a post-translational modification that occurs under conditions of oxidative stress. It is implicated in a variety of medical conditions, including neurodegenerative and cardiovascular diseases. However, monitoring tyrosine nitration and understanding its role in modifying biological function remains a major challenge. In this work, we investigate the use of electron-vibration-vibration (EVV) two-dimensional infrared (2DIR) spectroscopy for the study of tyrosine nitration in model peptides. We demonstrate the ability of EVV 2DIR spectroscopy to differentiate between the neutral and deprotonated states of 3-nitrotyrosine, and we characterize their spectral signatures using information obtained from quantum chemistry calculations and simulated EVV 2DIR spectra. To test the sensitivity of the technique, we use mixed-peptide samples containing various levels of tyrosine nitration, and we use mass spectrometry to independently verify the level of nitration. We conclude that EVV 2DIR spectroscopy is able to provide detailed spectroscopic information on peptide side-chain modifications and to detect nitration levels down to 1%. We further propose that lower nitration levels could be detected by introducing a resonant Raman probe step to increase the detection sensitivity of EVV 2DIR spectroscopy. (Graph Presented).

Supermode-noise suppression using a nonlinear Fabry–Pérot filter in a harmonically mode-locked fiber ring laser

A simple efficient method for stabilizing a harmonically mode-locked fiber ring laser is proposed. In this method, a linear optical filter and a nonlinear Fabry–Pérot filter in which the refractive index is optical intensity dependent are located in the laser cavity. The linear filter is used to select a fixed lasing wavelength, and the Fabry–Pérot filter introduces a negative all-optical feedback mechanism that is able to suppress pulse-to-pulse amplitude fluctuations in the laser cavity. The scheme was experimentally demonstrated using a fiber Bragg grating as the linear filter and a laser diode biased below threshold as the nonlinear Fabry–Pérot, and stable harmonically mode-locked pulses with a supermode noise suppression ratio >55 dB were obtained.

Noise suppression in a harmonically mode-locked fibre ring laser

A simple and efficient method to stabilise harmonically mode-locked fibre ring laser is proposed. In this method, a linear optical filter and a nonlinear Fabry-Perot filter are introduced into the laser cavity. Stable harmonically mode-locked pulses with supermode noise suppression ratio more than 55dB was demonstrated.

Optical loading sensor based on single polarization fiber laser incorporating an intra-cavity 45°-TFG

We have experimentally demonstrated an active loading sensor system based on a fiber ring laser with single-polarization output using an intra-cavity 45°-tilted fiber grating (45°-TFG). When the laser cavity fiber subjected to loading, the laser output is encoded with the load and can be measured and monitored by a power metre. A loading sensitivity as high as 0.033/ (kg·m-1) has been achieved using this laser. The experiment results clearly show that single polarization fiber laser may be developed to a low-cost high-sensitivity loading sensor system. © 2014 SPIE.

Multi-wavelength switchable fibre ring laser based on polarisation selective tilted fibre gratings capable of strain and temperature sensing

Using three fibre gratings with excessively tilted structures in the cavity, we have experimentally demonstrated a multiwavelength switchable erbium-doped fibre ring laser system. The three tilted gratings act as in-fibre polariser and polarisation dependent loss filters to induce the polarisation hole burning effect in the cavity for the operation of the laser at single, double, triple and quadruple wavelengths. The laser system has demonstrated good stability under room temperature conditions and also achieved a high degree of polarization (~30dB), high optical signal to noise ratio (up to 63dB) and high side mode suppression (~50dB). The system has also been investigated for temperature and strain sensing by subjecting the seeding fibre Bragg gratings (FBG) to temperature and strain variations. Since the loss band of the polarisation dependent loss filter is broader than the bandwidth of the seeding FBG, the laser output shifts in wavelength with the applied temperature and strain. The fibre ring laser has shown good responses to the temperature and strain, providing sensitivities of approximately 11.7 pm/°C and 0.85pm/µe respectively.

Higher-order soliton generation in hybrid mode-locked thulium-doped fiber ring laser

A thulium-doped all-fiber laser passively mode-locked by the co-action of nonlinear polarization evolution and single-walled carbon nanotubes operating at 1860-1980 nm wavelength band is demonstrated. Pumped with the single-mode laser diode at 1.55 μm laser generates near 500-fs soliton pulses at repetition rate ranging from 6.3 to 72.5 MHz in single-pulse operation regime. Having 3-m long cavity average output power reached 300 mW, giving the peak power of 4.88 kW and the pulse energy of 2.93 nJ with slope efficiency higher than 30%. At a 21.6-m long ring cavity average output power of 117 mW is obtained, corresponding to the pulse energy up to 10.87 nJ and a pulse peak power of 21.7 kW, leading to the higher-order soliton generation.

Resonance vector mode locking

A mode locked fibre laser as a source of ultra-stable pulse train has revolutionised a wide range of fundamental and applied research areas by offering high peak powers, high repetition rates, femtosecond range pulse widths and a narrow linewidth. However, further progress in linewidth narrowing seems to be limited by the complexity of the carrier-envelope phase control. Here for the first time we demonstrate experimentally and theoretically a new mechanism of resonance vector self-mode locking where tuning in-cavity birefringence leads to excitation of the longitudinal modes sidebands accompanied by the resonance phase locking of sidebands with the adjacent longitudinal modes. An additional resonance with acoustic phonons provides the repetition rate tunability and linewidth narrowing down to Hz range that drastically reduces the complexity of the carrier-envelope phase control and so will open the way to advance lasers in the context of applications in metrology, spectroscopy, microwave photonics, astronomy, and telecommunications.