Control of evanescent field using a dynamic waveguide composed of gelatin-coated few-layer fiber.

We report here the results of our studies on dynamic refractive-index (RI) profile few-layer fibers in view of controlling the mode-field profile, in particular the evanescent tails under varying structural configuration. We experimentally fabricate dynamic RI profile few-layer fibers using thin gelatin coating on selectively etched fibers and illustrate how the excitation of various modes and the evanescent field at the interface can be controlled with changing humidity parameter. As a technology outcome of this research, we demonstrate through an optimized structural configuration a well performing fiber-optic high (70%-98%) relative humidity (RH) sensor with sensitivity as high as -1.07 dBm/%RH.

Single all-optical platform for measurement of twist and transverse stress using polarization modulation in distinct dual-mode fiber placed in a Sagnac loop.

We report here the experimental demonstration of measurement of both twist and transverse stress using polarization modulation in a single all-fiber circuit consisting of a single-mode fiber (SMF)/dual-mode fiber (DMF) in a Sagnac interferometer (SI) loop. The SMF-SI prototype setup is seen to be suitable for precise measurement of twist over a broad range of ±50° and transverse stress up to 5 N with a sensitivity as high as 2.85×10(6) pW/° and 2.08×10(7) pW/N, respectively. It is envisaged that nearly ideal operation for twist measurement can be achieved by appropriately selecting the operating domain (pretwisted Sagnac loop for practical realization of the device) and required magnitude of applied transverse stress (weight yielding maximum sensitivity). Unlike SMF-SI, a DMF assisted SI exhibits asymmetric transmittance yielding a peak shift (∼45°) in addition to falling/rising peak amplitude of effective power(∼20 µW). This key characteristic is further utilized for tunable measurement of torsion (unidirectional from -70° to 40°) while keeping the sensitivity fixed. This research problem is then analyzed on the avenue of theoretical consideration and using classical polarization optics; we have derived the Jones birefringence matrix that accurately describes the transmission behavior of the configured fiber circuit (SMF-SI and DMF-SI) for each of the three cases, namely, transverse stress, twist, and both twist and transverse stress. Series of experimental measurements for various conditions of induced birefringence (linear/circular) were performed at length, and the results were compared with those determined theoretically towards configuring a twist and stress measuring device. The study provides an understanding of the underlying physics of dual-mode interference in a Sagnac configuration experiencing linear and circular birefringence.

Copper coordinated ligand thioether-S and NO2(-) oxidation: relevance to the CuM site of hydroxylases.

In order to gain insight into the coordination site and oxidative activity of the CuM site of hydroxylases such as peptidylglycine α-hydroxylating monooxygenase (PHM), dopamine ß-monooxygenase (DßM), and tyramine ß-monooxygenase (TßM), we have synthesized, characterized and studied the oxidation chemistry of copper complexes chelated by tridentate N2Sthioether, N2Osulfoxide or N2Osulfone donor sets. The ligands are those of N-2-methylthiophenyl-2'-pyridinecarboxamide (HL1), and the oxidized variants, N-2-methylsulfenatophenyl-2'-pyridinecarboxamide (HL1(SO)), and N-2-methylsulfinatophenyl-2'-pyridinecarboxamide (HL1(SO2)). Our studies afforded the complexes [(L1)Cu(II)(H2O)](ClO4)·H2O (1·H2O), {[(L1(SO))Cu(II)(CH3CN)](ClO4)}n (2), [(L1)Cu(II)(ONO)] (3), [(L1(SO))Cu(II)(ONO)]n (4), [(L1)Cu(II)(NO3)]n (5), [(L1(SO))Cu(II)(NO3)]n (6) and [(L1(SO2))Cu(II)(NO3)] (7). Complexes 1 and 3 were described in a previous publication (Inorg. Chem., 2013, 52, 11084). The X-ray crystal structures revealed either distorted octahedral (in 2, 4-6) or square-pyramidal (in 1, 3) coordination geometry around Cu(II) ions of the complexes. In the presence of H2O2, conversion of 1→2, 3-5→6 and 6→7 occurs quantitatively via oxidation of thioether-S and/or Cu(ii) coordinated NO2(-) ions. Thioether-S oxidation of L1 also occurs when [L1](-) is reacted with [Cu(I)(CH3CN)4](ClO4) in DMF under O2, albeit low in yield (20%). Oxidations of thioether-S and NO2(-) were monitored by UV-Vis spectroscopy. Recovery of the sulfur oxidized ligands from their metal complexes allowed for their characterization by elemental analysis, (1)H NMR, FTIR and mass spectrometry.

Polarization and propagation characteristics of switchable first-order azimuthally asymmetric beam generated in dual-mode fiber.

We report here the controlled generation of a linearly polarized first-order azimuthally asymmetric beam (F-AAB) in a dual-mode fiber (DMF) by appropriate superposition of selectively excited zeroth-order vector modes that are doughnut-shaped azimuthally symmetric beams (D-ASBs). We first demonstrate continually switching polarization mode structures having an identical two-lobe intensity profile (i.e., intra-F-AAB conversion). Then, under a distinct launching state, we generate mode structures progressively toggling between the doughnut-shaped profile and two-lobe pattern having dissimilar polarization orientations (i.e., F-AAB to D-ASB conversion). Interestingly, a decentralized elliptical Gaussian beam possessing homogenous spatial polarization is obtained by enhancing the contribution of the fundamental mode (HE11/LP01) in selectively excited F-AAB. A smoothly varying azimuth of the input beam in this situation resulted in redistribution of transverse energy procuring a unique and exciting unconventional two-grain T-polarized beam having mutually orthogonal state of polarization (SOP). All of the above three were achieved under a given set of launching conditions (tilt/offset) of a Gaussian mode (TEM00) devised with changing SOP of the input beam. A strong modulation in the output beam characteristics was also observed with the variation in propagation distance (for a fixed input SOP) owing to the large difference in propagation constants of the participating modes (LP01 and one of the F-AABs). Finally, this particular study led to a design for a low-cost highly sensitive strain measuring device based on tracking the centroid movement of the output intensity pattern. Each of our experimentally observed intensity/polarization distributions is theoretically mapped on a one-to-one basis considering a linear superposition of appropriately excited LP basis modes of the waveguide toward a complete understanding of the polarization and mode propagation in the dual-mode structure.

Hexacoordinate nickel(II)/(III) complexes that mimic the catalytic cycle of nickel superoxide dismutase.

A functional model complex of nickel superoxide dismutase (NiSOD) with a non-peptide ligand which mimics the full catalytic cycle of NiSOD is unknown. Similarly, it has not been fully elucidated whether NiSOD activity is a result of an outer- or inner-sphere electron-transfer mechanism. With this in mind, two octahedral nickel(II)/(III) complexes of a bis-tridentate N2 S donor carboxamide ligand, N-2-phenylthiophenyl-2'-pyridinecarboxamide (HL(Ph)), have been synthesized, structurally characterized, and their SOD activities examined. These complexes mimic the full catalytic cycle of NiSOD. Electrochemical experiments support an outer-sphere electron-transfer mechanism for their SOD activity.

Copper complexes relevant to the catalytic cycle of copper nitrite reductase: electrochemical detection of NO(g) evolution and flipping of NO2 binding mode upon Cu(II) → Cu(I) reduction.

Copper complexes of the deprotonated tridentate ligand, N-2-methylthiophenyl-2'-pyridinecarboxamide (HL1), were synthesized and characterized as part of our investigation into the reduction of copper(II) o-nitrito complexes into the related copper nitric oxide complexes and subsequent evolution of NO(g) such as occurs in the enzyme copper nitrite reductase. Our studies afforded the complexes [(L1)Cu(II)Cl]n (1), [(L1)Cu(II)(ONO)] (2), [(L1)Cu(II)(H2O)](ClO4)·H2O (3·H2O), [(L1)Cu(II)(CH3OH)](ClO4) (4), [(L1)Cu(II)(CH3CO2)]·H2O (5·H2O), and [Co(Cp)2][(L1)Cu(I)(NO2)(CH3CN)] (6). X-ray crystal structure determinations revealed distorted square-pyramidal coordination geometry around Cu(II) ion in 1-5. Substitution of the H2O of 3 by nitrite quantitatively forms 2, featuring the κ(2)-O,O binding mode of NO2(-) to Cu(II). Reduction of 2 generates two Cu(I) species, one with κ(1)-O and other with the κ(1)-N bonded NO2(-) group. The Cu(I) analogue of 2, compound 6, was synthesized. The FTIR spectrum of 6 reveals the presence of κ(1)-N bonded NO2(-). Constant potential electrolysis corresponding to Cu(II) → Cu(I) reduction of a CH3CN solution of 2 followed by reaction with acids, CH3CO2H or HClO4 generates 5 or 3, and NO(g), identified electrochemically. The isolated Cu(I) complex 6 independently evolves one equivalent of NO(g) upon reaction with acids. Production of NO(g) was confirmed by forming [Co(TPP)NO] in CH2Cl2 (λ(max) in CH2Cl2: 414 and 536 nm, ν(NO) = 1693 cm(-1)).

Shuttling of nickel oxidation states in N4S2 coordination geometry versus donor strength of tridentate N2S donor ligands.

Seven bis-Ni(II) complexes of a N(2)S donor set ligand have been synthesized and examined for their ability to stabilize Ni(0), Ni(I), Ni(II) and Ni(III) oxidation states. Compounds 1-5 consist of modifications of the pyridine ring of the tridentate Schiff base ligand, 2-pyridyl-N-(2'-methylthiophenyl)methyleneimine ((X)L1), where X = 6-H, 6-Me, 6-p-ClPh, 6-Br, 5-Br; compound 6 is the reduced amine form (L2); compound 7 is the amide analog (L3). The compounds are perchlorate salts except for 7, which is neutral. Complexes 1 and 3-7 have been structurally characterized. Their coordination geometry is distorted octahedral. In the case of 6, the tridentate ligand coordinates in a facial manner, whereas the remaining complexes display meridional coordination. Due to substitution of the pyridine ring of (X)L1, the Ni-N(py) distances for 1~5 < 3 < 4 increase and UV-vis λ(max) values corresponding to the (3)A(2g)(F)→(3)T(2g)(F) transition show an increasing trend 1~5 < 2 < 3 < 4. Cyclic voltammetry of 1-5 reveals two quasi-reversible reduction waves that correspond to Ni(II)→Ni(I) and Ni(I)→Ni(0) reduction. The E(1/2) for the Ni(II)/Ni(I) couple decreases as 1 > 2 > 3 > 4. Replacement of the central imine N donor in 1 by amine 6 or amide 7 N donors reveals that complex 6 in CH(3)CN exhibits an irreversible reductive response at E(pc) = -1.28 V, E(pa) = +0.25 V vs saturated calomel electrode (SCE). In contrast, complex 7 shows a reversible oxidation wave at E(1/2) = +0.84 V (ΔE(p) = 60 mV) that corresponds to Ni(II)→Ni(III). The electrochemically generated Ni(III) species, [(L3)(2)Ni(III)](+) is stable, showing a new UV-vis band at 470 nm. EPR measurements have also been carried out.