Epoxide ring opening in a zinc(II) complex in water without any Lewis acid catalyst: formation of only one diastereomer out of 2

The epoxide ring in 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) opens up in its reaction with 4-methylaniline and 4-methoxyaniline in water in equimolar proportion at room temperature without any Lewis acid catalyst to give a monohydrate of 6-(4-methyl-phenylamino)-5,6-dihydro-1,10-phenanthrolin-5-ol (L′·H2O) and 6-(4-methoxyphenyl-amino)-5,6-dihydro-1,10-phenanthrolin-5-ol (L″) respectively. Reaction time decreases from 72 to 14 h in boiling water. But the yields become less. Reaction of L with Zn(ClO4)2·6H2O in methanol in 3:1 molar ratio at room temperature affords white [ZnL3](ClO4)2·H2O. The X-ray crystal structure of the acetonitrile solvate [ZnL3](ClO4)2·MeCN has been determined which shows that the metal has a distorted octahedral N6 coordination sphere. [ZnL3](ClO4)2·2H2O reacts with 4-methylaniline and 4-methoxyaniline in boiling water in 1:3 molar proportion in the absence of any Lewis acid catalyst to produce [ZnL′3](ClO4)2·4H2O and [ZnL″3](ClO4)2·H2O, respectively in 1–4 h time in somewhat low yield. In the 1H NMR spectra of [ZnL′3](ClO4)2·4H2O and [ZnL″3](ClO4)2·H2O, only one sharp methyl signal is observed implicating that only one diastereomer out of the 23 possibilities is formed. The same diastereomers are obtained when L′·H2O and L″ are reacted directly with Zn(ClO4)2·6H2O in tetrahydrofuran at room temperature in very good yields. Reactions of L′·H2O and L″ with Ru(phen)2Cl2·2H2O (phen = 1,10-phenanthroline) in equimolar proportion in methanol–water mixture under refluxing condition lead to the isolation of two diastereomers of [Ru(phen)2L′](ClO4)2·2H2O and [Ru(phen)2L″](ClO4)2·2H2O.

Characterization of para-Nitrophenol-degrading bacterial communities in river water by using functional markers and stable isotope probing

Microbial degradation is a major determinant of the fate of pollutants in the environment. para-Nitrophenol (PNP) is an EPA listed priority pollutant with a wide environmental distribution, but little is known about the microorganisms that degrade it in the environment. We studied the diversity of active PNP-degrading bacterial populations in river water using a novel functional marker approach coupled with [13C6]PNP stable isotope probing (SIP). Culturing together with culture-independent terminal restriction fragment length polymorphism analysis of 16S rRNA gene amplicons identified Pseudomonas syringae to be the major driver of PNP degradation in river water microcosms. This was confirmed by SIP-pyrosequencing of amplified 16S rRNA. Similarly, functional gene analysis showed that degradation followed the Gram-negative bacterial pathway and involved pnpA from Pseudomonas spp. However, analysis of maleylacetate reductase (encoded by mar), an enzyme common to late stages of both Gram-negative and Gram-positive bacterial PNP degradation pathways, identified a diverse assemblage of bacteria associated with PNP degradation, suggesting that mar has limited use as a specific marker of PNP biodegradation. Both the pnpA and mar genes were detected in a PNP-degrading isolate, P. syringae AKHD2, which was isolated from river water. Our results suggest that PNP-degrading cultures of Pseudomonas spp. are representative of environmental PNP-degrading populations.

Estimation using 18O of the water residence time in small watersheds

From the 18O hydrograph separation method, it was found that groundwater contribution is the principal component of the total discharge produced by these two catchment areas. The weighted mean of the 18O concentration in the precipitation, obtained for a four year period, was close to -6.0‰, with a variation in range of +2.3‰ to -16.3‰. For Bufalos stream water the weighted mean of 18O values during the same period (1984-1987) was -6.3‰, with a variation from -2.5‰ to -10.1‰, whereas for Paraiso this mean was -6.4‰, with extreme values of -3.1‰ and -9.8‰. From these values it was found that the amplitude damping (Ariver/Aprecipitation) was 0.41 for the Bufalos watershed and 0.36 for Paraiso. Using the appropriate equation to estimate the mean residence time of water in the subsurface reservoir of the Bufalos and Paraiso watersheds, the results of 4.3 and 5.0 months, respectively, were obtained. -from Authors

A trophic study of the sympatric Amazonian freshwater turtles Podocnemis unifilis and Podocnemis expansa (Testudines, Podocnemidae) using carbon and nitrogen stable isotope analyses

The Yellow-spotted River Turtle (Podocnemis unifilis Troschel, 1848) and the South American River Turtle (Podocnemis expansa (Schweigger, 1812)) are two turtles species that are widely distributed and have ecological, economic, and cultural importance in the Amazon basin. Although sympatric regarding most of their distribution, few studies have addressed the coexistence of these two species. To examine this, we analyzed the trophic level and the primary carbon source from the diets of both species in Baixo Araguaia, Tocantins, Brazil, using stable isotope analyses of carbon (delta C-13) and nitrogen (delta N-15). We also verified possible intraspecific variations (related to sex and body mass) in the trophic levels and primary carbon sources of their diets. Podocnemis unifilis had higher values of delta N-15 than P. expansa, averaging 7.59 parts per thousand and 5.06 parts per thousand, respectively, a difference which may indicate a possible trophic change owing to exploiting different food resources. No differences were found between the two species in relation to delta C-13 (mean values of -26.2 parts per thousand and -26.1 parts per thousand, respectively). The similarity between delta C-13 values suggests that the sources of their basal feeding are the same, consisting mainly of C-3 plants. There was no intraspecific variation in the values of delta C-13 and delta N-15.

Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have chan- ged the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (13C, 15N, 18O) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2–8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water heptamer, (H2O)7, in both 2– 8 GHz and 6–18 GHz frequency ranges. Two isomers of the water heptamer have been observed in a pulsed supersonic molecular expansion. High level ab initio structural searches were performed to pro- vide plausible low-energy candidates which were directly compared with accurate structures provided from broadband rotational spectra. The full substitution structure of the most stable species has been obtained through the analysis of all possible singly-substituted isotopologues (H218O and HDO), and a least-squares rm(1) geometry of the oxygen framework determined from 16 different isotopic species compares with the calculated O–O equilibrium distances at the 0.01 Å level.

Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have changed the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (C-13, N-15, O-18) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2-8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water heptamer, (H2O)(7), in both 2-8 GHz and 6-18 GHz frequency ranges. Two isomers of the water heptamer have been observed in a pulsed supersonic molecular expansion. High level ab initio structural searches were performed to provide plausible low-energy candidates which were directly compared with accurate structures provided from broadband rotational spectra. The full substitution structure of the most stable species has been obtained through the analysis of all possible singly-substituted isotopologues ((H2O)-O-18 and HDO), and a least-squares r(m)((1)) geometry of the oxygen framework determined from 16 different isotopic species compares with the calculated O-O equilibrium distances at the 0.01 angstrom level. (C) 2013 Elsevier B.V. All rights reserved.

The Assessment of Total Energy Expenditure During a 14-day 'In-Season' Period of Professional Rugby League Players Using the Doubly Labelled Water Method

Peer reviewed

Comparative Histopathological Analysis of Human Pulps after Class I Cavity Preparation with a High-Speed Air-Turbine Handpiece or Er:YAG Laser

The purpose of this study was to comparatively evaluate the response of human pulps after cavity preparation with different devices. Deep class I cavities were prepared in sound mandibular premolars using either a high-speed air-turbine handpiece (Group 1) or an Er: YAG laser (Group 2). Following total acid etching and the application of an adhesive system, all cavities were restored with composite resin. Fifteen days after the clinical procedure, the teeth were extracted and processed for analysis under optical microscopy. In Group 1 in which the average for the remaining dentin thickness (RDT) between the cavity floor and the coronal pulp was 909.5 mu m, a discrete inflammatory response occurred in only one specimen with an RDT of 214 mu m. However, tissue disorganization occurred in most specimens. In Group 2 (average RDT = 935.2 mu m), the discrete inflammatory pulp response was observed in only one specimen (average RDT = 413 mu m). It may be concluded that the high-speed air-turbine handpiece caused greater structural alterations in the pulp, although without inducing inflammatory processes.

Comparative Histopathological Analysis of Human Pulps after Class I Cavity Preparation with a High-Speed Air-Turbine Handpiece or Er:YAG Laser

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Numerical modeling of fiber lasers with long and ultra-long ring cavity

We highlight two important aspects related to a mathematical modeling of pulsed fiber lasers with long and ultra-long ring cavity -impact of an initial noise and a cavity length on generation of single optical pulses. Using as an example a simple scalar model of a ring fiber laser that describes the radiation build-up from noise and the following intra-cavity pulse dynamics during a round trip we study dependence of generated pulse characteristics on the resonator length in the range from 30 m up to 2 km. © 2013 Optical Society of America.

Tunable diode Laser Absorption Spectroscopy ,Nir Overtone and Life Studies of Some Organic Compound

The present work is mainly concentrated on setting up a NIR tunable diode laser absorption (TDLA) spectrometer for high-resolution molecular spectroscopic studies. For successfully recording the high-resolution tunable diode laser spectrum, various experimental considerations are to be taken into account like the setup should be free from mechanical vibrations, sample should be kept at a low pressure, laser should be in a single mode operation etc. The present experimental set up considers all these factors. It is to be mentioned here that the setting up of a high resolution NIR TDLA spectrometer is a novel experiment requiring much effort and patience. The analysis of near infrared (NIR) vibrational overtone spectra of some substituted benzene compounds using local mode model forms another part of the present work. An attempt is made to record the pulsed laser induced fluorescence/Raman spectra of some organic compounds. A Q-switched Nd:YAG laser is used as the excitation source. A TRIAX monochromator and CCD detector is used for the spectral recording. The observed fluorescence emission for carbon disulphide is centered at 680 nm; this is assigned as due to the n, p* transition. Aniline also shows a broad fluorescence emission centered at 725 nm, which is due to the p,p* transition. The pulsed laser Raman spectra of some organic compounds are also recorded using the same experimental setup. The calibration of the set up is done using the laser Raman spectra of carbon tetrachloride and carbon disulphide. The observed laser Raman spectra for aniline, o-chloroaniline and m-chlorotoluene show peaks characteristics of the aromatic ring in common and the characteristics peaks due to the substitutuent groups. Some new peaks corresponding to low-lying vibrations of these molecules are also assigned

Highly Sensitive Sensor Based On Intracavity Laser Absorption Spectroscopy By Means of Relative Intensity Noise

This thesis concerns with the main aspects of medical trace molecules detection by means of intracavity laser absorption spectroscopy (ICLAS), namely with the equirements for highly sensitive, highly selective, low price, and compact size sensor. A novel two modes semiconductor laser sensor is demonstrated. Its operation principle is based on the competition between these two modes. The sensor sensitivity is improved when the sample is placed inside the two modes laser cavity, and the competition between the two modes exists. The effects of the mode competition in ICLAS are discussed theoretically and experimentally. The sensor selectivity is enhanced using external cavity diode laser (ECDL) configuration, where the tuning range only depends on the external cavity configuration. In order to considerably reduce the sensor cost, relative intensity noise (RIN) is chosen for monitoring the intensity ratio of the two modes. RIN is found to be an excellent indicator for the two modes intensity ratio variations which strongly supports the sensor methodology. On the other hand, it has been found that, wavelength tuning has no effect on the RIN spectrum which is very beneficial for the proposed detection principle. In order to use the sensor for medical applications, the absorption line of an anesthetic sample, propofol, is measured. Propofol has been dissolved in various solvents. RIN has been chosen to monitor the sensor response. From the measured spectra, the sensor sensitivity enhancement factor is found to be of the order of 10^(3) times of the conventional laser spectroscopy.

Long-lived excited-state dynamics of i-motif structures probed by time-resolved infrared spectroscopy

UV-generated excited states of cytosine (C) nucleobases are precursors to mutagenic photoproduct formation. The i-motif formed from C-rich sequences is known to exhibit high yields of long-lived excited states following UV absorption. Here the excited states of several i-motif structures have been characterized following 267 nm laser excitation using time-resolved infrared spectroscopy (TRIR). All structures possess a long-lived excited state of ~300 ps and notably in some cases decays greater than 1 ns are observed. These unusually long-lived lifetimes are attributed to the interdigitated DNA structure which prevents direct base stacking overlap.