Resonance Raman and lifetime studies on regioselectively deuteriated ruthenium (II) polypyridyl complexes

Two series of ruthenium(II) polypyridyl complexes [Ru(bipy)2(phpytr)]+ and [Ru(bipy)2(phpztr)]+ (where Hphpytr = 2-(5-phenyl-1H-[1,2,4]triazol-3-yl)-pyridine and Hphpztr = 2-(5-phenyl-1H-[1,2,4]triazol-3-yl)-pyrazine) are examined by electrochemistry, UV/Vis, emission, resonance Raman, transient resonance Raman and transient absorption spectroscopy, in order to obtain a more comprehensive understanding of their excited state electronic properties. The interpretation of the results obtained is facilitated by the availability of several isotopologues of each of the complexes examined. For the pyridine-1,2,4-triazolato based complex the lowest emissive excited state is exclusively bipy based, however, for the pyrazine based complexes excited state localisation on particular ligands shows considerable solvent and pH dependency.

Paralytic shellfish poisoning detection by surface plasmon resonance-based biosensors in shellfish matrixes.

The detection of paralytic shellfish poisoning (PSP) toxins in contaminated shellfish is essential for human health preservation. Ethical and technical reasons have prompted the search for new detection procedures as an alternative to the mouse bioassay. On the basis of the detection of molecular interactions by surface plasmon resonance (SPR) biosensors, an inhibition assay was developed using an anti-GTX2/3 antibody (GT13-A) and a saxitoxin-CM5 chip. This assay allowed for quantification of saxitoxin (STX), decarbamoyl saxitoxin (dcSTX), gonyautoxin 2,3 (GTX2/3), decarbamoyl gonyautoxin 2,3 (dcGTX2/3), gonyautoxin 5 (GTX5), and C 1,2 (C1/2) at concentrations from 2 to 50 ng/mL. The interference of five shellfish matrixes with the inhibition assay was analyzed. Mussels, clams, cockles, scallops, and oysters were extracted with five published methods. Ethanol extracts and acetic acid/heat extracts (AOAC Lawrence method) performed adequately in terms of surface regeneration and baseline interference, did not inhibit antibody binding to the chip surface significantly, and presented STX calibration curves similar to buffer controls in all matrixes tested. Hydrochloric acid/heat extracts (AOAC mouse bioassay method) presented surface regeneration problems, and although ethanol-acetic acid/dichloromethane extracts performed well, they were considered too laborious for routine sample testing. Overall the best results were obtained with the ethanol extraction method with calibration curves prepared in blank matrix extracts. STX recovery rate with the ethanol extraction method was 60.52 ± 3.72%, with variations among species. The performance of this biosensor assay in natural samples, compared to two AOAC methods for PSP toxin quantification (mouse bioassay and HPLC), suggests that this technology can be useful as a PSP screening assay. In summary, the GT13-A-STX chip inhibition assay is capable of PSP toxin detection in ethanol shellfish extracts, with sufficient sensitivity to quantify the toxin in the range of the European regulatory limit of 80 g/100 g of shellfish meat.

Proton Formation in 2+1 Resonance Enhanced Multiphoton Excitation of HCl and HBr via „=0… Rydberg and Ion-Pair States

Molecular beam cooled HCl was state selected by two-photon excitation of the V (1) summation operator(0(+)) [v=9,11-13,15], E (1) summation operator(0(+)) [v=0], and g (3) summation operator(-)(0(+)) [v=0] states through either the Q(0) or Q(1) lines of the respective (1,3) summation operator(0(+))<--<--X (1) summation operator(0(+)) transition. Similarly, HBr was excited to the V (1) summation operator(0(+)) [v=m+3, m+5-m+8], E (1) summation operator(0(+)) [v=0], and H (1) summation operator(0(+)) [v=0] states through the Q(0) or Q(1) lines. Following absorption of a third photon, protons were formed by three different mechanisms and detected using velocity map imaging. (1) H(*)(n=2) was formed in coincidence with (2)P(i) halogen atoms and subsequently ionized. For HCl, photodissociation into H(*)(n=2)+Cl((2)P(12)) was dominant over the formation of Cl((2)P(32)) and was attributed to parallel excitation of the repulsive [(2) (2)Pi4llambda] superexcited (Omega=0) states. For HBr, the Br((2)P(32))Br((2)P(12)) ratio decreases with increasing excitation energy. This indicates that both the [(3) (2)Pi(12)5llambda] and the [B (2) summation operator5llambda] superexcited (Omega=0) states contribute to the formation of H(*)(n=2). (2) For selected intermediate states HCl was found to dissociate into the H(+)+Cl(-) ion pair with over 20% relative yield. A mechanism is proposed by which a bound [A (2) summation operatornlsigma] (1) summation operator(0(+)) superexcited state acts as a gateway state to dissociation into the ion pair. (3) For all intermediate states, protons were formed by dissociation of HX(+)[v(+)] following a parallel, DeltaOmega=0, excitation. The quantum yield for the dissociation process was obtained using previously reported photoionization efficiency data and was found to peak at v(+)=6-7 for HCl and v(+)=12 for HBr. This is consistent with excitation of the repulsive A(2) summation operator(12) and (2) (2)Pi states of HCl(+), and the (3) (2)Pi state of HBr(+). Rotational alignment of the Omega=0(+) intermediate states is evident from the angular distribution of the excited H(*)(n=2) photofragments. This effect has been observed previously and was used here to verify the reliability of the measured spatial anisotropy parameters.

The resonance spectrum of the cusp map in the space of analytic functions

We prove that the Frobenius-Perron operator $U$ of the cusp map $F:[-1,1]\to [-1,1]$, $F(x)=1-2 x^{1/2}$ (which is an approximation of the Poincare section of the Lorenz attractor) has no analytic eigenfunctions corresponding to eigenvalues different from 0 and 1. We also prove that for any $q\in (0,1)$ the spectrum of $U$ in the Hardy space in the disk $\{z\in C:|z-q|

A surface plasmon resonance biosensor assay for the simultaneous determination of thiamphenicol, florefenicol, florefenicol amine and chloramphenicol residues in shrimps

A rapid and sensitive screening qualitative method using a surface plasmon resonance (SPR) biosensor was developed which can detect of all fenicol antibiotic residues in shrimps from a single sample extract. This method requires ethyl acetate extraction followed by a single wash with isooctane/chlorofonrm. Each sample extract is injected over the surfaces of two biosensor chip flow cells, one surface having the capability to detect florefenicol amine (FF amine), florefenicol (FF), and thiamphenicol (TAP) and the second surface for chloramphenicol (CAP) detection. The estimated detection capabilities (CC beta) were 0. 1, 0.2, 250, and 0.5 ppb for CAP, FF, FF amine, and TAP, respectively. This quick, simple test allowed the detection of CAP residues in shrimps at the minimum required performance limit (MRPL) of 0.1 mu g kg(-1) for this compound and of FF, FF amine, and TAP below their maximum residue limits (MRLs). (c) 2006 Elsevier B.V. All rights reserved.

Resonance Raman and DFT studies of tetra-tert-butyl porphine: Assignment of strongly enhanced distortion modes in a ruffled porphyrin

The free-base form of tetra-tert-butyl porphine (TtBP), which has extremely bulky meso substituents, is severely distorted from planarity, with a ruffling angle of 65.5degrees. The resonance Raman spectrum of TtBP (lambda(ex) = 457.9 nm) and its d(2), d(8), and d(10) isotopomers have been recorded, and while the spectra show high-frequency bands similar to those observed for planar meso-substituted porphyrins, there are several additional intense bands in the low-frequency region. Density functional calculations at the B3-LYP/6-31G(d) level were carried out for all four isotopomers, and calculated frequencies were scaled using a single factor of 0.98. The single factor scaling approach was validated on free base porphine where the RMS error was found to be 14.9 cm(-1). All the assigned bands in the high-frequency (> 1000 cm(-1)) region of TtBP were found to be due to vibrations similar in character to the in-plane skeletal modes of conventional planar porphyrins. In the low-frequency region, two of the bands, assigned as nu(8) (ca. 330 cm(-1)) and nu(16) (ca. 540 cm(-1)), are also found in planar porphyrins such as tetra-phenyl porphine (TPP) and tetra-iso-propyl porphine (IPP). Of the remaining three very strong bands, the lowest frequency band was assigned as gamma(12) (pyr swivel, obsd 415 cm(-1), calcd 407 cm(-1) in do). The next band, observed at 589 cm-1 in the do compound (calcd 583 cm(-1)), was assigned as a mode whose composition is a mixture of modes that were previously labeled gamma(13) (gamma(CmCaHmCa)) andy gamma(11) (pyr fold(asym)) in NiOEP. The final strong band, observed at 744 cm(-1) (calcd 746 cm(-1)), was assigned to a mode whose composition is again a mixture of gamma(11) and gamma(13), although here it is gamma(11) rather than gamma(13) which predominates. These bands have characters and positions similar to those of three of the four porphyrin ring-based, weak bands that have previously been observed for NiTPP. In addition there are several weaker bands in the TtBP spectra that are also

Control-limited perfect state transfer, quantum stochastic resonance, and many-body entangling gate in imperfect qubit registers

We propose a protocol for perfect quantum state transfer that is resilient to a broad class of realistic experimental imperfections, including noise sources that could be modeled either as independent Markovian baths or as certain forms of spatially correlated environments. We highlight interesting connections between the fidelity of state transfer and quantum stochastic resonance effects. The scheme is flexible enough to act as an effective entangling gate for the generation of genuine multipartite entanglement in a control-limited setting. Possible experimental implementations using superconducting qubits are also briefly discussed.