Isotopic evidence for condensed aromatics from non-pyrogenic sources in soils--implications for current methods for quantifying soil black carbon

Black carbon (BC) is a complex continuum of partly charred organic matter predominantly consisting of condensed aromatic and graphitic moieties and it has high potential for long-term carbon sequestration in soils and sediments. There has been common agreement that BC is exclusively formed by incomplete combustion of organic matter, while non-pyrogenic sources are negligible. In this study, we investigated the stable carbon isotope signature of benzenepolycarboxylic acids (BPCAs) as molecular markers for BC to test if there is also a significant contribution of non-pyrogenic carbon to this fraction in soils. BPCAs were formed by hot nitric acid oxidation of different soils and analyzed by three different procedures: (i) elemental analysis - isotope ratio mass spectrometry (EA-IRMS) of bulk BPCAs and gas chromatography - combustion - isotope ratio mass spectrometry (GC-C-IRMS) of (ii) BPCA trimethylsilyl (TMS) derivatives, and (iii) BPCA methyl derivatives. Best accuracy and precision of isotope measurements were obtained by EA-IRMS of bulk BPCAs although this method has a risk of contamination by non-BC-derived compounds. The accuracy and precision of GC-C-IRMS measurements were superior for methyl derivatives (+/-0.1 per thousand and 0.5 per thousand, respectively) to those for TMS derivatives (+3.5 per thousand and 2.2 per thousand, respectively).Comparison of BPCA delta(13)C values of soil samples prior to and after laboratory and field incubations with both positive and negative (13)C labels at natural and artificial abundances revealed that up to 25% of the isolated BC fraction in soils had been produced in situ, without fire or charring. Commonly applied methods to quantify BC exclusively formed by pyrogenic processes may thus be biased by a significant non-pyrogenic fraction. Further research is encouraged to better define isolated BC fractions and/or understand mechanisms for non-pyrogenic BC production in soils.     

Molecular and electronic structures of mononuclear iron complexes using strongly electron-donating ligands and their oxidized forms

The ligand L (2-) (H 2L = N, N'-dimethyl- N, N'-bis(3,5-di- t-butyl-2-hydroxybenzyl)-1,2-diaminoethane) has been employed for the synthesis of two mononuclear Fe (III) complexes, namely, [LFe(eta (2)-NO 3)] and [LFeCl]. L (2-) is comprised of four strongly electron-donating groups (two tert-amines and two phenolates) that increase the electron density at the coordinated ferric ions. This property should facilitate oxidation of the complexes, that is, stabilization of the oxidized species. The molecular structures in the solid state have been established by X-ray diffraction studies. [LFeCl] is five-coordinate in a square-pyramidal coordination environment with the ligand adopting a trans-conformation, while [LFe(eta (2)-NO 3)] is six-coordinate in a distorted octahedral environment with the ligand in a beta-cis conformation. The electronic structures have been studied using magnetization, EPR, Mossbauer (with and without applied field), UV-vis-NIR, and X-ray absorption spectroscopies, which demonstrate highly anisotropic covalency from the strong sigma- and pi-donating phenolates. This analysis is supported by DFT calculations on [LFeCl]. The variations of the well-understood spectroscopic data in the solid state to the spectroscopic data in solution have been used to obtain insight in the molecular structure of the two complexes in solution. While the molecular structures of the solid states are retained in solutions of nonpolar aprotic solvents, there is, however, one common molecular structure in all protic polar solvents. The analysis of the LMCT transitions and the rhombicity E/ D clearly establish that both compounds exhibit a beta-cis conformation in these protic polar solvents. These two open coordination sites, cis to each other, allow access for two potential ligands in close proximity. Electrochemical analysis establishes two reversible oxidation waves for [LFeCl] at +0.55 V and +0.93 V vs Fc (+)/Fc and one reversible oxidation wave at +0.59 V with an irreversible oxidation at +1.07 V vs Fc (+)/Fc for [LFe(eta (2)-NO 3)]. The one- and the two-electron oxidations of [LFeCl] by chronoamperometry have been followed spectroscopically. The increase of a strong band centered at 420 nm indicates the formulation of [LFeCl] (+) as a Fe (III) monophenoxyl radical complex and of [LFeCl] (2+) as a Fe (III) bisphenoxyl radical complex. These studies imply that the ligand L (2-) is capable of providing a flexible coordination geometry with two binding sites for substrates and the allocation of two oxidation equivalents on the ligand.     

Electronic structures and spin topologies of gamma-picoliniumyl radicals. A study of the homolysis of N-methyl-gamma-picolinium and of benzo-, dibenzo-, and naphthoannulated analogs

Radicals resulting from one-electron reduction of (N-methylpyridinium-4-yl) methyl esters have been reported to yield (N-methylpyridinium-4-yl) methyl radical, or N-methyl-gamma-picoliniumyl for short, by heterolytic cleavage of carboxylate. This new reaction could provide the foundation for a new structural class of bioreductively activated, hypoxia-selective antitumor agents. N-methyl-gamma-picoliniumyl radicals are likely to damage DNA by way of H-abstraction and it is of paramount significance to assess their H-abstraction capabilities. In this context, the benzylic C-H homolyses were studied of toluene (T), gamma-picoline (P, 4-methylpyridine), and N-methyl-gamma-picolinium (1c, 1,4-dimethylpyridinium). With a view to providing capacity for DNA intercalation the properties also were examined of the annulated derivatives 2c (1,4-dimethylquinolinium), 3c (9,10-dimethylacridinium), and 4c (1,4-dimethylbenzo[g]quinolinium). The benzylic C-H homolyses were studied with density functional theory (DFT), perturbation theory (up to MP4SDTQ), and configuration interaction methods (QCISD(T), CCSD(T)). Although there are many similarities between the results obtained here with DFT and CI theory, a number of significant differences occur and these are shown to be caused by methodological differences in the spin density distributions of the radicals. The quality of the wave functions is established by demonstration of internal consistencies and with reference to a number of observable quantities. The analysis of spin polarization emphasizes the need for a clear distinction between "electron delocalization" and "spin delocalization" in annulated radicals. Aside from their relevance for the rational design of new antitumor drugs, the conceptional insights presented here also will inform the understanding of ferromagnetic materials, of spin-based signaling processes, and of spin topologies in metalloenzymes.     

Nitrosation chemistry of pyrroline, 2-imidazoline, and 2-oxazoline: theoretical Curtin-Hammett analysis of retro-ene and solvent-assisted C-X cleavage reactions of alpha-hydroxy-N-nitrosamines

The results are presented of a theoretical study of the nitrosation chemistry of pyrroline 1 (X = CH2), imidazoline 2 (X = NH), and 2-oxazoline 3 (X = O). Imines 1-3 are converted to the alpha-hydroxy-N-nitrosamines 7-9 via the N-nitrosoiminium ions 4-6. The NN-cis isomers of 7-9 may undergo retro-ene reactions to the delta-oxoalkyl diazotic acids 10-12. With the opportunity for microsolvation, C-X cleavage becomes possible for 8 and 9 and leads to the formation of N-(2-aminoethyl)- and N-(2-hydroxyethyl)-N-nitrosoformamides 15 and 16, respectively. The NN-isomerization barriers are comparable to the barriers for the ring-opening reactions, and the consideration of two Curtin-Hammett scenarios is required: CH-I for the NN-trans-rotamers of 7-9 to undergo C-X cleavage or NN-isomerization and CH-II for the NN-cis-rotamers to undergo C-X cleavage, C-N cleavage, or NN-isomerization. We determined all stereoisomers of the substrates, the products, and of all transition states structures for the retro-ene reactions of 7-9, the C-X cleavages of microsolvated 8 and 9, and the NN-isomerizations of 8 and 9. The potential energy surfaces were explored at the B3LYP/6-31G level, and the results are discussed with emphasis on the comparison of the kinetics and thermodynamics of C-N versus C-X cleavage. The study shows all decompositions to be very fast with activation barriers below 21 kcal.mol(-1), and the comparative analysis predicts that the chemical toxicologies of 1 and 3 should be similar and remarkably different from that of 2.     

Pattern pulses: design of arbitrary excitation profiles as a function of pulse amplitude and offset

A novel class of pulses is presented which can be regarded as a generalization of both frequency-selective pulses and B1-selective pulses. The excitation profile of these pulses forms a pre-defined pattern in two dimensions, which are spanned by pulse offset and radio-frequency (RF) amplitude. The presented pulses were designed numerically based on principles of optimal control theory. For simple test patterns, we demonstrate the flexibility of this approach by simulations and experiments. This previously unknown flexibility may trigger novel applications in NMR spectroscopy and imaging. As a first practical application, we demonstrate a direct approach for calibrating RF pulses.     

Scopolamine and atropineN-methyl diastereomer stability.Ab initio calculations onO-formylscopine andO-formyltropine model compounds

Ab initio geometry optimizations at the RHF-21G basis set level were calculated forequatorial andaxial N-methyl diastereomers ofO-formyltropine andO-formylscopine esters and other model compounds. These optimized geometries were then utilized as input for single-point energy calculations using the higher level RHF/6-31G^* basis set to afford a more precise estimation of the total energies and atomic charges. Ethano bridge pinching of theN-protonated tropanyl piperidine moiety pushes the smalleraxial N-proton closer toward the neighboring twoaxial C-H bonds compared with the analogous case for a bulkyaxial N-methyl. Increasedcis 1,3-diaxial interactions in theaxial N-methyl diastereomer destabilize this epimer in favor of theequatorial N-methyl counterpart [e.g., 2.121 kcal/mol lower energy for theequatorial N-methylO-formyltropineN-protonated diastereomer (12) than for theaxial epimer (13)]. Lower pyramidality at nitrogen in the free base maintains the relative stability of theequatorial N-methyl free base diastereomer (14) (1.120 kcal/mol more stable than theaxial free base15). A nonprotonated carbon atom at the apex of a three-membered ring fused to the 6,7-positions of theO-formyltropine skeleton results in severe transannular nonbonding steric interactions involving the neighboringequatorial N-methyl group inN-protonated16 (3.335 kcal/mol less stable than theaxial N-methyl epimer17, where these transannular interactions are reduced due to the smallerequatorial N-H proton). Oxygen atom occupation of the apex of a similar fused three-membered ring retains the same severe transannular nonbonding steric interactions involving the neighboringequatorial N-methyl group inN-protonated18. These transannular interactions now become electrostatically attractive in theN-protonatedaxial N-methyl epimer19 (2.031 kcal/mol more stable than theequatorial epimer). Reduced pyramidality at nitrogen in theO-formylscopine free base reduces the repulsive transannular interaction with the neighboringequatorial N-methyl group compared to that in theN-protonated form. Lowered pyramidality also reduces thecis-1,3-diaxial interactions in theaxial N-methyl epimer, but the nitrogen lone pair is pushed close to the transannular oxygen lone pair as a result (theequatorial N-methyl free base20 is 3.870 kcal/mol more stable than theaxial epimer21). Theseab initio-calculated models ofO-formyltropines andO-formylscopineN-methyl diastereomeric protonated cations and free bases provide stereochemical insight into the relative stabilities of solution-state atropine and scopolamineN-methyl species previously observed by NMR spectroscopic methods.