Colorimetric Detection of Aqueous N-Nitrosodimethylamine via Photonitrosation of a Naphtholsulfonate Indicator.

N-Nitrosamines are contaminants found throughout the environment, including in drinking water, and many nitrosamines are likely potent carcinogens. Correspondingly, there is a need for rapid and cost-effective in-field detection methods that can provide timely information about their contamination levels in water. This study details a colorimetric assay for detecting aqueous N-nitrosodimethylamine (NDMA) by photochemical nitrosation of a commercial naphtholsulfonate, to offer an attractive alternative to traditional laboratory-based analysis. The resulting naphthoquinone-oxime coordinates to aqueous iron(II) ions to form a green complex, allowing for direct visual detection. Characterization via Mössbauer and electron paramagnetic resonance (EPR) spectroscopy, alongside single-crystal structure determination, provides comprehensive structure information on the iron indicator complex. Optimization of detection conditions, including UV irradiation and response times, led to an improved colorimetric detection method with a limit of detection of 0.66 ppm for NDMA. The practical applicability and selectivity of this colorimetric detection scheme make it a promising candidate for the development of field-deployable sensors for NDMA in environmental water samples.

A general method for metallocluster site-differentiation.

The deployment of metalloclusters in applications such as catalysis and materials synthesis requires robust methods for site-differentiation: the conversion of clusters with symmetric ligand spheres to those with unsymmetrical ligand spheres. However, imparting precise patterns of site-differentiation is challenging because, compared with mononuclear complexes, the ligands bound to clusters exert limited spatial and electronic influence on one another. Here, we report a method that employs sterically encumbering ligands to bind to only a subset of a cluster's coordination sites. Specifically, we show that homoleptic, phosphine-ligated Fe-S clusters undergo ligand substitution with N-heterocyclic carbenes (NHCs) to give heteroleptic clusters in which the resultant clusters' site-differentiation patterns are encoded by the steric profile of the incoming NHC. This method affords access to every site-differentiation pattern for cuboidal [Fe4S4] clusters and can be extended to other cluster types, particularly in the stereoselective synthesis of site-differentiated Chevrel-type [Fe6S8] clusters.

The Elusive Mononitrosylated [Fe4 S4 ] Cluster in Three Redox States.

Iron-sulfur clusters are well-established targets in biological nitric oxide (NO) chemistry, but the key intermediate in these processes-a mononitrosylated [Fe4 S4 ] cluster-has not been fully characterized in a protein or a synthetic model thereof. Here, we report the synthesis of a three-member redox series of isostructural mononitrosylated [Fe4 S4 ] clusters. Mononitrosylation was achieved by binding NO to a 3 : 1 site-differentiated [Fe4 S4 ]+ cluster; subsequent oxidation and reduction afforded the other members of the series. All three clusters feature a local high-spin Fe3+ center antiferromagnetically coupled to 3 [NO]- . The observation of an anionic NO ligand suggests that NO binding is accompanied by formal electron transfer from the cluster to NO. Preliminary reactivity studies with the monocationic cluster demonstrate that exposure to excess NO degrades the cluster, supporting the intermediacy of mononitrosylated intermediates in NO sensing/signaling.

A Terminal Imido Complex of an Iron-Sulfur Cluster.

We report the synthesis and characterization of the first terminal imido complex of an Fe-S cluster, (IMes)3 Fe4 S4 =NDipp (2; IMes=1,3-dimesitylimidazol-2-ylidene, Dipp=2,6-diisopropylphenyl), which is generated by oxidative group transfer from DippN3 to the all-ferrous cluster (IMes)3 Fe4 S4 (PPh3 ). This two-electron process is achieved by formal one-electron oxidation of the imido-bound Fe site and one-electron oxidation of two IMes-bound Fe sites. Structural, spectroscopic, and computational studies establish that the Fe-imido site is best described as a high-spin Fe3+ center, which is manifested in its long Fe-N(imido) distance of 1.763(2) Å. Cluster 2 abstracts hydrogen atoms from 1,4-cyclohexadiene to yield the corresponding anilido complex, demonstrating competency for C-H activation.

An [Fe4S4]3+-Alkyl Cluster Stabilized by an Expanded Scorpionate Ligand.

Alkyl-ligated iron-sulfur clusters in the [Fe4S4]3+ charge state have been proposed as short-lived intermediates in a number of enzymatic reactions. To better understand the properties of these intermediates, we have prepared and characterized the first synthetic [Fe4S4]3+-alkyl cluster. Isolation of this highly reactive species was made possible by the development of an expanded scorpionate ligand suited to the encapsulation of cuboidal clusters. Like the proposed enzymatic intermediates, this synthetic [Fe4S4]3+-alkyl cluster adopts an S = 1/2 ground state with giso > 2. Mössbauer spectroscopic studies reveal that the alkylated Fe has an unusually low isomer shift, which reflects the highly covalent Fe-C bond and the localization of Fe3+ at the alkylated site in the solid state. Paramagnetic 1H NMR studies establish that this valence localization persists in solution at physiologically relevant temperatures, an effect that has not been observed for [Fe4S4]3+ clusters outside of a protein. These findings establish the unusual electronic-structure effects imparted by the strong-field alkyl ligand and lay the foundation for understanding the electronic structures of [Fe4S4]3+-alkyl intermediates in biology.

Nanoscale surface tracking of laser material processing using phase shifting diffraction interferometry.

Phase shifting diffraction interferometry (PSDI) was adapted to provide real-time feedback control of a laser-based chemical vapor deposition (LCVD) process with nanometer scale sensitivity. PSDI measurements of laser heated BK7 and fused silica substrates were used to validate a finite element model that accounts for both refractive index changes and displacement contributions to the material response. Utilizing PSDI and accounting for the kinetics of the modeled thermomechanical response, increased control of the LCVD process was obtained. This approach to surface tracking is useful in applications where extreme environments on the working surface require back-side optical probing through the substrate.

First multi-watt ribbon fiber oscillator in a high order mode.

Optical fibers in the ribbon geometry have the potential to reach powers well above the maximum anticipated power of a circular core fiber. In this paper we report the first doped silica high order mode ribbon fiber oscillator, with multimode power above 40 W with 71% slope efficiency and power in a single high order mode above 5 W with 44% slope efficiency.

First selective mode excitation and amplification in a ribbon core optical fiber.

We propose and demonstrate amplification of a single high-order mode in an optical fiber having an elongated, ribbon-like core having an effective mode area of area of 600 µm(2) and an aspect ratio of 13:1. When operated as an amplifier, the double-clad, ytterbium doped, photonic crystal fiber produced 50% slope efficiency and a seed-limited power of 10.5 W, corresponding to a gain of 24 dB. The high order mode remained pure through 20 dB of gain without intervention or realignment.

Mode-converters for rectangular-core fiber amplifiers to achieve diffraction-limited power scaling.

A rectangular-core (ribbon) fiber that guides and amplifies a single higher-order-mode (HOM) can potentially scale to much higher average powers than what is possible in traditional circular-core large-mode-area fibers. Such an amplifier would require mode-conversion at the input to enable interfacing with seed sources that typically output TEM(00) mode radiation and at the output to generate diffraction-limited radiation for end-user applications. We present the first simulation and experimental results of a mode conversion technique that uses two diffractive-optic-elements in conjugate Fourier planes to convert a diffraction limited TEM(00) mode to the HOM of a ribbon fiber. Mode-conversion-efficiency is approximately 84% and can theoretically approach 100%. We also demonstrate a mode-converter system that converts a single HOM of a ribbon fiber back to a diffraction-limited TEM(00) mode. Conversion efficiency is a record 80.5%.

Mode conversion in rectangular-core optical fibers.

Mode conversion from the fundamental to a higher-order mode in a rectangular-core optical fiber is accomplished by applying pressure with the edge of a flat plate. Modal analysis of the near and far field images of the fiber's transmitted beam determines the purity of the converted mode. Mode conversion reaching 75% of the targeted higher-order mode is achieved using this technique. Conversion from a higher-order mode back to the fundamental mode is also demonstrated with comparable efficiency. Propagation of a higher-order mode in a rectangular-core fiber allows for better thermal management and bend-loss immunity than conventional circular-core fibers, extending the power-handling capabilities of optical fibers.

High brightness, quantum-defect-limited conversion efficiency in cladding-pumped Raman fiber amplifiers and oscillators.

We present a detailed theoretical investigation of cladding-pumped Raman fiber amplification in an unexplored parameter space of high conversion efficiency (> 60%) and high brightness enhancement (> 1000). Fibers with large clad-to-core diameter ratios can provide a promising means for Raman-based brightness enhancement of diode pump sources. Unfortunately, the diameter ratio cannot be extended indefinitely since the intensity generated in the core can greatly exceed that in the cladding long before the pump is fully depleted. If left uncontrolled, this leads to the generation of parasitic second-order Stokes wavelengths in the core, limiting the conversion efficiency and as we will show, clamping the achievable brightness enhancement. Using a coupled-wave formalism, we present the upper limit on brightness enhancement as a function of diameter ratio for conventionally guided fibers. We further present strategies for overcoming this limit based upon depressed well core designs. We consider two configurations: 1) pulsed cladding-pumped Raman fiber amplifier (CPRFA) and 2) cw cladding-pumped Raman fiber laser (CPRFL).

Brightness enhancement in a high-peak-power cladding-pumped Raman fiber amplifier.

We demonstrate a cladding-pumped Raman fiber amplifier (CPRFA) whose brightness-enhancement factor depends on the cladding-to-core diameter ratio. The pump and the signal are coupled independently into different input arms of a pump-signal combiner, and the output is spliced to the Raman amplifier fiber. The CPRFA generates 20 microJ, 7 ns pulses at 1100 nm at a 2.2 kHz repetition rate with 300 microJ (25.1 kW peak power) of input pump energy. The amplified signal's peak power is 2.77 kW, and the brightness-enhancement factor is 192--the highest peak power and brightness enhancement achieved in a CPRFA at any wavelength, to our knowledge.

High-gain photonic crystal fiber regenerative amplifier.

We have demonstrated a photonic crystal fiber-based regenerative amplifier at 1.078 microm. The input signal pulse energy is 20 pJ in a 12 ns pulse at a 3 kHz repetition rate. At 8.6 W of input pump power, the amplified output pulse energy is 157 microJ, yielding a gain of 69 dB. To our knowledge, this is the highest gain achieved in a fiber-based regenerative amplifier to date at any wavelength.

Analysis of the scalability of diffraction-limited fiber lasers and amplifiers to high average power.

We analyze the scalability of diffraction-limited fiber lasers considering thermal, non-linear, damage and pump coupling limits as well as fiber mode field diameter (MFD) restrictions. We derive new general relationships based upon practical considerations. Our analysis shows that if the fiber's MFD could be increased arbitrarily, 36 kW of power could be obtained with diffraction-limited quality from a fiber laser or amplifier. This power limit is determined by thermal and non-linear limits that combine to prevent further power scaling, irrespective of increases in mode size. However, limits to the scaling of the MFD may restrict fiber lasers to lower output powers.

Zigzag slabs for solid-state laser amplifiers: batch fabrication and parasitic oscillation suppression.

We have developed a 100 W class Nd:YAG master oscillator power amplifier system based in part on an end-pumped zigzag slab power amplifier. This amplifier incorporates parasitic oscillation suppression by using roughened edges and achieves a small-signal gain coefficient (g(0)l) of 8.06. We describe a novel technique for suppression of parasitic oscillations using claddings on slab edges that significantly increases g(0)l to 11.63 and increases the single-pass extracted power in a power amplifier by 50%. Commercial use of these zigzag slab amplifiers has been limited by the time and cost of production. We describe a new batch fabrication technique that improves the quality and significantly reduces the cost of zigzag slabs.

Disk motion ??? a new control element in high-brightness solid state laser design.

The brightness of cw and quasi cw solid state lasers of conventional designs is limited by stress fracture and uncorrectable phase aberration in thermally loaded stationary gain medium. By introducing physical motion of the gain medium as a new control element in the design of solid state lasers, we show the potential to significantly increase the brightness of cw and quasi cw solid state lasers. In this paper, we develop the design equations of rotary disk lasers and illustrate the design of a 1-kilowatt single mode Yb-YAG rotary disk laser.