IntCal04 terrestrial radiocarbon age calibration, 0-26 cal kyr BP

A new calibration curve for the conversion of radiocarbon ages to calibrated (cal) ages has been constructed and internationally ratified to replace IntCal98, which extended from 0-24 cal kyr BP (Before Present, 0 cal BP = AD 1950). The new calibration data set for terrestrial samples extends from 0-26 cal kyr BP, but with much higher resolution beyond 11.4 cal kyr BP than IntCal98. Dendrochronologically-dated tree-ring samples cover the period from 0-12.4 cal kyr BP. Beyond the end of the tree rings, data from marine records (corals and foraminifera) are converted to the atmospheric equivalent with a site-specific marine reservoir correction to provide terrestrial calibration from 12.4-26.0 cal kyr BP. A substantial enhancement relative to IntCal98 is the introduction of a coherent statistical approach based on a random walk model, which takes into account the uncertainty in both the calendar age and the (super 14) C age to calculate the underlying calibration curve (Buck and Blackwell, this issue). The tree-ring data sets, sources of uncertainty, and regional offsets are discussed here. The marine data sets and calibration curve for marine samples from the surface mixed layer (Marine04) are discussed in brief, but details are presented in Hughen et al. (this issue a). We do not make a recommendation for calibration beyond 26 cal kyr BP at this time; however, potential calibration data sets are compared in another paper (van der Plicht et al., this issue).

Optical diagnostics of micro discharge jets

Micro plasmas operated at ambient pressure with dimensions of the confining geometry in the order of a few ten micrometers to a millimeter are actually in the focus of interest due to the broad regime of applicability they offer and due to a similarly broad range of open physical questions. Here we present optical measurements within the discharge core and the effluent region of an especially developed micro discharge jet. To get an understanding of the complex system of this discharge it is important to analyse transport phenomena of energy and particles within both parts of the discharge by various highly sophisticated diagnostics. As a consequence of the limited access and the dimensions of the micro discharge most of these diagnostics are optical. Here we present diagnostics applied to determine spatially resolved absolute atomic oxygen densities as the most reactive constituent of the effluent, density maps of ozone as final reaction product of the gas chemical chain induced by the discharge and phase resolved optical emission spectroscopy yielding insight into the excitation dynamics of the discharge. (C) 2007 WILEY-VCH Verlag GmbH & Co. KGaA. Weinheim.

Effect of solution pH, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon

The adsorption behavior of C.I. Reactive Blue 2, C.I. Reactive Red 4, and C.I. Reactive Yellow 2 from aqueous solution onto activated carbon was investigated under various experimental conditions. The adsorption capacity of activated carbon for reactive dyes was found to be relatively high. At pH 7.0 and 298 K, the maximum adsorption capacity for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes was found to be 0.27, 0.24, and 0.11 mmol/g, respectively. The shape of the adsorption isotherms indicated an L2-type isotherm according to the Giles and Smith classification. The experimental adsorption data showed good correlation with the Langmuir and Ferundlich isotherm models. Further analysis indicated that the formation of a complete monolayer was not achieved, with the fraction of surface coverage found to be 0.45, 0.42, and 0.22 for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes, respectively. Experimental data indicated that the adsorption capacity of activated carbon for the dyes was higher in acidic rather than in basic solutions, and further indicated that the removal of dye increased with increase in the ionic strength of solution, this was attributed to aggregation of reactive dyes in solution. Thermodynamic studies indicated that the adsorption of reactive dyes onto activated carbon was an endothermic process. The adsorption enthalpy (?H) for C.I. Reactive Blue 2 and C.I. Reactive Yellow 2 dyes were calculated at 42.2 and 36.2 kJ/mol, respectively. The negative values of free energy (?G) determined for these systems indicated that adsorption of reactive dyes was spontaneous at the temperatures under investigation (298-328 K). © 2007 Elsevier Ltd. All rights reserved.

IntCal09 and Marine09 radiocarbon age calibration curves, 0 - 50,000 years cal BP

The IntCal04 and Marine04 radiocarbon calibration curves have been updated from 12 cal kBP (cal kBP is here defined as thousands of calibrated years before AD 1950), and extended to 50 cal kBP, utilizing newly available data sets that meet the IntCal Working Group criteria for pristine corals and other carbonates and for quantification of uncertainty in both the ¹⁴C and calendar timescales as established in 2002. No change was made to the curves from 0-12 cal kBP. The curves were constructed using a Markov chain Monte Carlo (MCMC) implementation of the random walk model used for IntCal04 and Marine04. The new curves were ratified at the 20th International Radiocarbon Conference in June 2009 and are available in the Supplemental Material at www.radiocarbon.org.

Asymmetric rhodium carbene insertion into the Si-H bond: identification of new dirhodium(II) carboxylate catalysts using parallel synthesis techniques

Decomposition of methyl 2-diazophenylacetate in the presence of silanes and a chiral dirhodium(11) catalyst results in Si-H insertion of the intermediate carbenoid with varying degrees of enantioselectivity. New chiral dirhodium(11) carboxylate catalysts were identified using solution phase parallel synthesis techniques. (C) 2003 Elsevier Science Ltd. All rights reserved.

The carbenoid approach to peptide synthesis

A different approach to the synthesis of dipeptides is described based on the formation of the (NHCHRCONH)-C-1-(CHRCO)-C-2 bond by carbenoid N-H insertion, rather than the formation of the peptide bond itself. Thus decomposition of triethyl diazophosphonoacetate catalysed by rhodium(Ii) acetate in the presence of N-protected amino acid amides 8 gives the phosphonates 9, Subsequent Wadsworth-Emmons reaction of 9 with aldehydes in the presence of DBU gives dehydro dipeptides 10. The reaction has been extended to a simple two-step procedure, without the isolation of the intermediate phosphonate. for conversion of a range of amino acid amides 11 into dehydro dipepides 12 and to an N-methylamide 11h, and for conversion of a dipeptide: to tripeptide (13-14). Direct conversion, by using methyl diazophenylacetate, of amino acid amides to phenylglycine-containing dipeptides 19 proceeds in good chemical yield, but with poor diastereoselectivity.

N-H insertion reactions of rhodium carbenoids. Part 1. Preparation of  -amino acid and  -aminophosphonic acid derivatives.

Rh(II) acetate-catalyzed decompn. of diazophenylacetates PhC(N2)CO2Me 1 and PhC(N2)CO2R* 3 [R*OH = (-)-borneol, (+)-menthol, (-)-8-phenylmenthol] in the presence of a range of N-H compds. results in an N-H insertion reaction of the intermediate carbenoids and formation of N-substituted phenylglycine derivs. PhCH(NR1R2)CO2Me 2 [R1 = R2 = Et; R1 = 4-MeOC6H4, COCH2CHMe2, CO2CH2Ph, (S)-CH(CO2Me)CH2Ph, (S)-CHMePh, R2 = H; 64-83% yields] and PhCH(NR1R2)CO2R* 4 (R1 = R2 = Et; R1 = COMe, CO2Me, R2 = H; same R*; 37-71% yields). The corresponding reactions of di-Me ?-diazobenzylphosphonate PhC(N2)P(O)(OMe)2 5 with primary amines constitute a simple route to aminophosphonates PhCH(NHR)P(O)(OMe)2 6 (R = COMe, COEt, CO2CH2Ph, CO2CMe3, 4-ClC6H4, 4-MeC6H4, 4-MeOC6H4; 13-96% yields).

Asymmetric rhodium carbenoid insertion into the Si-H bond.

Buck, Richard T.; Doyle, Michael P.; Drysdale, Martin J.; Ferris, Leigh; Forbes, David C.; Haigh, David; Moody, Christopher J.; Pearson, Neil D.; Zhou, Qi-Lin. Dep. Chemistry, Loughborough Univ., Loughborough, Leicestershire, UK. Tetrahedron Letters (1996), 37(42), 7631-7634. Publisher: Elsevier, CODEN: TELEAY ISSN: 0040-4039. Journal written in English. CAN 125:328854 AN 1996:644681 CAPLUS (Copyright (C) 2009 ACS on SciFinder (R)) Abstract Decompn. of Me 2-diazophenylacetate in the presence of dimethylphenylsilane and a chiral dirhodium(II) catalyst results in Si-H insertion of the intermediate carbenoid to give PhCH(SiMe2Ph)CO2Me with varying degrees of enantioselectivity (up to 47% ee; 47% using (S)-Rh2L4, LH = I).