Properties of laser-induced stimulated emission for diagnostic purposes

We describe an experimental and semi-quantitative theoretical investigation of the characteristics of two-photon-induced stimulated emission related to diagnostic applications. The laser power dependence, pressure dependence, and the spectral shape of the stimulated emission signal in CO are discussed and compared with those for laser-induced fluorescence. We also discuss decreases in the laser-induced fluorescence signal caused by the stimulated emission process, and propose a method for providing increased spatial resolution in measurements made using stimulated emission detection.This work was supported by the Swedish National Board for Technical Developments, the Swedish Energy Administration, and the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences     

Voltage of the vacuum arc with a ring anode in an axial magneticfield

The plasma jet focusing and voltage distribution in the interelectrode gap of a vacuum arc with a ring anode and subjected to an axial magnetic field were studied theoretically. A two-dimensional model was developed based on the free plasma jet expansion into vacuum, and the steady-state solution of the fully ionized plasma in the hydrodynamic approximation was analyzed. It was found that the imposition of an axial magnetic field reduces the radial expansion of the plasma jet. The characteristic jet angle decreases from about 40° in the zero magnetic field case and approaches a value of about 20° with a 0.02 T magnetic field. The arc voltage consisting of the cathode drop, the plasma voltage drop, and anode sheath drop increased, with the imposition of a magnetic field, and decreased with the anode length. The model was compared to experimental measurements of the vacuum arc voltage behavior in an axial magnetic field, and good agreement was found     

The polarographic behaviour of the 1,4-benzodiazepines, oxazepam and lorazepam, and a method for quality control

The polarographic behaviour of the drugs, oxazepam and lorazepam, has been investigated over a wide pH range. Different types of wave are obtained depending on the pH. The pK_a, values calculated are in good agreement with those obtained from u.v. spectroscopic measurements. For analytical purposes, the optimal pH is 4.7 (acetate supporting electrolyte), the 4-electron reduction wave being measured. A quality control method for the two drugs in different formulations containing 0.5–15 mg of active constituent is described.     

C-H activation by a mononuclear manganese(III) hydroxide complex: synthesis and characterization of a manganese-lipoxygenase mimic?

Lipoxygenases are mononuclear non-heme metalloenzymes that regio- and stereospecifically convert 1,4-pentadiene subunit-containing fatty acids into alkyl peroxides. The rate-determining step is generally accepted to be hydrogen atom abstraction from the pentadiene subunit of the substrate by an active metal(III)-hydroxide species to give a metal(II)-water species and an organic radical. All known plant and animal lipoxygenases contain iron as the active metal; recently, however, manganese was found to be the active metal in a fungal lipoxygenase. Reported here are the synthesis and characterization of a mononuclear Mn(III) complex, [Mn(III)(PY5)(OH)](CF(3)SO(3))(2) (PY5 = 2,6-bis(bis(2-pyridyl)methoxymethane)pyridine), that reacts with hydrocarbon substrates in a manner most consistent with hydrogen atom abstraction and provides chemical precedence for the proposed reaction mechanism. The neutral penta-pyridyl ligation of PY5 endows a strong Lewis acidic character to the metal center allowing the Mn(III) compound to perform this oxidation chemistry. Thermodynamic analysis of [Mn(III)(PY5)(OH)](2+) and the reduced product, [Mn(II)(PY5)(H(2)O)](2+), estimates the strength of the O-H bond in the metal-bound water in the Mn(II) complex to be 82 (+/-2) kcal mol(-)(1), slightly less than that of the O-H bond in the related reduced iron complex, [Fe(II)(PY5)(MeOH)](2+). [Mn(III)(PY5)(OH)](2+) reacts with hydrocarbon substrates at rates comparable to those of the analogous [Fe(III)(PY5)(OMe)](2+) at 323 K. The crystal structure of [Mn(III)(PY5)(OH)](2+) displays Jahn-Teller distortions that are absent in [Mn(II)(PY5)(H(2)O)](2+), notably a compression along the Mn(III)-OH axis. Consequently, a large internal structural reorganization is anticipated for hydrogen atom transfer, which may be correlated to the lessened dependence of the rate of substrate oxidation on the substrate bond dissociation energy as compared to other metal complexes. The results presented here suggest that manganese is a viable metal for lipoxygenase activity and that, with similar coordination spheres, iron and manganese can oxidize substrates through a similar mechanism.     

Mechanism‐Guided Improvements to the Single Molecule Oxidation of Carbon Nanotube Sidewalls

Real‐time monitoring of carbon nanotube conductance during electrochemical and chemical etching reveals the electronic signatures of individual bond alteration events on the nanotube sidewall. Tracking the conductance of multiple single‐molecule experiments through different synthetic protocols supports putative mechanisms for sidewall derivatization. Insights gained from these mechanistic observations imply the formation of sidewall carboxylates, which are useful as handles for bioconjugation. We describe an electronic state required for efficacious chemical treatment. Such real‐time monitoring can improve carboxylate yields to 45 % or more. The experiments illustrate the power of molecular nanocircuits to uncover and direct the mechanisms of chemical reactions.     

Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters

The use of isotope ratio infrared spectroscopy (IRIS) for the stable hydrogen and oxygen isotope analysis of water is increasing. While IRIS has many advantages over traditional isotope ratio mass spectrometry (IRMS), it may also be prone to errors that do not impact upon IRMS analyses. Of particular concern is the potential for contaminants in the water sample to interfere with the spectroscopy, thus leading to erroneous stable isotope data. Water extracted from plant and soil samples may often contain organic contaminants. The extent to which contaminants may interfere with IRIS and thus impact upon data quality is presently unknown. We tested the performance of IRIS relative to IRMS for water extracted from 11 plant species and one organic soil horizon. IRIS deviated considerably from IRMS for over half of the samples tested, with deviations as large as 46‰ (δ²H) and 15.4‰ (δ¹⁸O) being measured. This effect was reduced somewhat by using activated charcoal to remove organics from the water; however, deviations as large as 35‰ (δ²H) and 11.8‰ (δ¹⁸O) were still measured for these cleaned samples. Interestingly, the use of activated charcoal to clean water samples had less effect than previously thought for IRMS analyses. Our data show that extreme caution is required when using IRIS to analyse water samples that may contain organic contaminants. We suggest that the development of new cleaning techniques for removing organic contaminants together with instrument‐based software to flag potentially problematic samples are necessary to ensure accurate plant and soil water analyses using IRIS. Copyright © 2010 John Wiley & Sons, Ltd.     

The Hopfian exponent of an abelian group

If \(G\) is a Hopfian abelian group then it is, in general, difficult to determine if direct sums of copies of \(G\) will remain Hopfian. We exhibit large classes of Hopfian groups such that every finite direct sum of copies of the group is Hopfian. We also show that for any integer \(n > 1\) there is a torsion-free Hopfian group \(G\) having the property that the direct sum of \(n\) copies of \(G\) is not Hopfian but the direct sum of any lesser number of copies is Hopfian.     

6-methylpyridyl for pyridyl substitution tunes the properties of fluorescent zinc sensors of the Zinpyr family

To prepare fluorescent zinc sensors with binding affinities lower than that of the parent 9-(o-carboxyphenyl)-2,7-dichloro-4,5-bis(bis(2-pyridylmethyl)methylaminomethyl)-6-hydroxy-3-xanthenone (ZP1), dimethylated and tetramethylated derivatives were synthesized having either two or four of the pyridyl subunits methylated at the 6-position. Like the parent ZP1, both Me(2)ZP1 and Me(4)ZP1 exhibit increased fluorescence in the presence of Zn(2+). The integrated emission of Me(2)ZP1 increases 4-fold in the presence of excess zinc, whereas Me(4)ZP1 displays 2.5-fold enhanced fluorescence for Zn(2+). Methylating the 6-positions of the pyridyl rings raises the dissociation constant of the sensors and lowers the pK(a) values associated with the tertiary amine ligands in a systematic manner. The properties of the dimethylated Me(2)ZP1 dye resemble those of ZP1, but the tetramethylated Me(4)ZP1 differs greatly from ZP1 in terms of its brightness, affinity toward Zn(2+), exchange kinetics, and metal sensitivity. Both Me(2)ZP1 and Me(4)ZP1 can enter HeLa cells and signal the presence of Zn(2+). Staining caused by both dyes is punctate, with localization patterns resembling that observed for ZP1.