Chemical Changes During 6 Years of Decomposition of 11 Litters in Some Canadian Forest Sites. Part 1. Elemental Composition, Tannins, Phenolics, and Proximate Fractions

Slowing or even cessation of litter decomposition with time is well-known, but there is insufficient understanding of the chemical changes that contribute to increasing recalcitrance. Samples from the Canadian Intersite Decomposition Experiment (CIDET) were used to determine 6-year chemical changes for all 11 litters from a site with rapid initial decomposition (Morgan Arboretum, MAR) and for three litters at three colder sites. Six-year mass remaining was 17–37% at MAR, with higher values at the colder sites. Atomic C/N ratios declined and phenolics and condensed tannins generally decreased to minimal values. However, for the three species compared across four sites, phenolics and tannins showed small increases for species with the lowest initial values and also tended to increase with increasing mass loss. For the foliar litters at MAR, there was an average increase in proportion of acid-unhydrolyzable residue (AUR) and decreases in proportions of acid-hydrolyzable (ACID) and extractable fractions, with final AUR/(ACID + AUR) ratios within 0.55–0.66. Principal component analysis showed that foliar litters (and to a lesser extent wood) became more alike after 6 years, decomposition being associated with increase of Fe, Al, N, and AUR concentrations and decrease of K, Mg, tannins, phenolics, and non-polar and water-soluble fractions. However, litters were also affected by site soil chemistry, with some high 6-year accumulations of Ca, Mg, Fe, Al, Mn, and Mg at two sites. Increasing recalcitrance likely arises from increasing dominance of complex, less-soluble organic structures, collectively represented by AUR, together with increases in heavy elements such as Al and Fe, which also specifically bind and stabilize organic matter.     

Metabolic Changes Detected by Ex Vivo High Resolution 1H NMR Spectroscopy in the Striatum of 6-OHDA-Induced Parkinson’s Rat

Parkinson’s disease (PD) is a neurodegenerative disorder characterized by the progressive loss of the dopaminergic neurons; however, its crucial mechanism of the metabolic changes of neurotransmitters remains ambiguous. The pathological mechanism of PD might involve cerebral metabolism perturbations. In this study, ex vivo proton nuclear magnetic resonance (¹H NMR) was used to determine the level changes of 13 metabolites in the bilateral striatum of 6-hydroxydopamine (6-OHDA)-induced PD rats. The results showed that, in the right striatum of 6-OHDA-induced PD rats, increased levels of glutamate (Glu) and γ-aminobutyric acid (GABA) concomitantly with decreased level of glutamine (Gln) were observed compared to the control. Whereas, in the left striatum of 6-OHDA-induced PD rats, increased level of Glu with decreased level of GABA and unchanged Gln were observed. Other cerebral metabolites including lactate, alanine, creatine, succinate, taurine, and glycine were also found to have some perturbations. The observed metabolic changes for Glu, Gln, and GABA are mostly likely the result of a shift in the steady-state equilibrium of the Gln-Glu-GABA metabolic cycle between astrocytes and neurons. The altered Gln and GABA levels are most likely as a strategy to protect neurons from Glu excitotoxic injury after striatal dopamine depletion. Changes in energy metabolism and tricarboxylic acid cycle might be involved in the pathogenesis of PD.     

On the Application of t-Butyldimethylsilyl Group in Chemical RNA Synthesis. Part I. 31P NMR Study of 2′-O-t-BDMSi Group Migration During Nucleoside 3′-OH Phosphorylation and Phosphitylation Reactions

Abstract

³¹P NMR spectroscopy has been used for evaluation of 2′-O-t-BDMSi group migration during reactions of suitably protected 3′-OH ribonucleosides with P(V) and P(III) reagents used in major methodologies for oligoribonucleotide synthesis.     

Changes in the δ13C values of trees during a tropical rainy season: some effects in addition to diffusion and carboxylation by rubisco?

The d13C values of deciduous and evergreen tree leaves were compared in open and closed- canopy environments throughout a rainy season in Panamá. Newly emerging leaves had higher d13C values than older leaves of all seedlings and trees at all dates sampled. This was apparently not caused by a decline in water use efficiency as leaves develop because instantaneous ci/ca was significantly higher in newly emerging than in expanded leaves on the same twigs of trees in the field as well as on seedlings growing in a controlled, unchanging environment. Higher d13C values in newly emerging leaves occurred across diverse environmental comparisons. For example, leaves emerging during the rainy season had higher d13C values than corresponding mature leaves that had emerged both during the dry season and when water was abundant. The early enrichment in 13C may thus reflect the translocation of carbon to initiate a new leaf. Furthermore, the lack of sensitivity of this enrichment to a microclimate suggests that it might be the result of processes that occur after carbon fixation by Rubisco. Other changes in d13C values as leaves developed may also have resulted from carbon translocation processes. Foliar d13C decreased significantly after most of the leaf biomass of the deciduous Apeiba membranacea had developed. The d13C values of the evergreen Cecropia insignis were lower in the open canopy than in closed-canopy forests at the end of the rainy season. These findings suggest that the d13C values of leaves can yield ecological information about the allocation of carbon within trees.     

The palaeoenvironments of coastal lagoons in the southern Baltic Sea,II. δ13C and δ15N ratios of organic matter — sources and sediments

Organic carbon and nitrogen isotope values (δ¹³C, δ¹⁵N) and C/N ratios of six sediment cores from six coastal lagoons (including the Oder Estuary) were measured to chart the coastal development and to reconstruct the local palaeoenvironments of the southern Baltic Sea region during the Holocene. In addition, δ¹³C, δ¹⁵N and C/N values of major organic matter sources in the coastal lagoons and their drainage areas are investigated to determine the origin of organic matter (i.e. terrigenous or marine) in the sediments: plankton, aquatic macrophytes, typical C3 shore plants and peat. The δ¹³C, δ¹⁵N and C/N values of the samples collected show the clearly identifiable stages in the development of the water bodies: post-glacial lake stages with sandy sedimentation, lacustrine phases with high autochthonous productivity, terrestrial stages with peat formation, sedimentation as a result of marine transgression, and brackish sedimentation after the formation of sand spits and barrier islands. These stages are the results of sea level changes in the region. The values allow derivation of differences in the palaeoenvironments of the lagoons in the study area. A distinct terrestrial input is evident in the sediments of the lagoonal Oder Estuary, which can be attributed to the direct inflow of the Oder River into the lagoon. The isotope and C/N values also suggest a contribution of C4 plant detritus for the water bodies in the northeastern part of the study area (Barther Bodden, Grabow). The burial of autochthonous organic matter (i.e. plankton, aquatic macrophytes) in the sediment could be derived for all lagoons in this investigation.     

Synthesis of heterodinuclear FeRu(CO)6(R-DAB(6e))(R-DABRNC(H)C(H)NR) Part XV. Comparison of the reactivities of heterodinuclear FeRu(CO)6(R-DAB(6e)) and homodinuclear analogues M2(CO)6(R-DAB(6e)) (M = Fe,Ru). Single-crystal x-ray structures of FeRu(CO)6(i-Pr-DAB(6e)) and FeRu(CO)5(i-Pr-DAB(4e))(C3H4)

The reactions of Fe(CO)₃(R-DAB; R¹, H(4e)) (1a: R = i-Pr, R¹ = H; 1b: R = t-Bu, R¹ = H; 1c: R = c-Hex, R¹ = H; 1e: R = p-Tol, R¹ = H; 1f: R = i-Pr, R¹ = Me) with Ru₃(CO)₁₂ and of Ru(CO)₃(R-DAB; R¹, H(4e)) (2a: R = i-Pr, R¹ = H; 2d: R = CH(i-Pr)₂, R¹ = H) with Fe₂(CO)₉ in refluxing heptane both afforded FeRu(CO)₆(R-DAB; R¹, H(6e)) (3) in yields between 50 and 65%.The coordination mode of the ligand has been studied by a single crystal X-ray structure determination of FeRu(CO)₆(i-Pr-DAB(6e)) (3a). Crystals of 3a are monoclinic, space group P2₁/a, with four molecules in a unit cell of dimensions: a = 22.436(3), b = 8.136(3), c = 10.266(1) Å and β = 99.57(1)°. The structure was refined to R = 0.049 and R_w = 0.052 using 3045 reflections above the 2.5σ(I) level. The molecule contains an FeRu bond of 2.6602(9) Å, three terminally bonded carbonyls to Fe, three terminally bonded carbonyls to Ru and bridging 6e donating i-Pr-DAB ligand. The i-Pr-DAB ligand is coordinated to Ru via N(1) and N(2) occupying an apical and equatorial site respectively (RuN(1) = 2.138(4) RuN(2) = 2.102(3) Å). The C(2)N(2) moiety of the ligand is η²-coordinated to Fe with C(2) in an apical and N(2) in an equatorial site (FeC(2) = 2.070(5) and FeN(2) = 1.942(3) Å).The ¹H and ¹³C NMR data indicate that in all FeRu(CO)₆(R-DAB(6e)) complexes (3a to 3f) exclusively η²-CN coordination to the Fe atom and not to the Ru atom is present irrespective of whether 3 was prepared by reaction of Fe(CO)₃(R-DAB(4e)) (1) with Ru₃(CO)₁₂ or by reaction of Ru(CO)₃(R-DAB(4e)) (2) with Fe₂(CO)₉. In the case of FeRu(CO)₆(i-Pr-DAB; Me, H(6e)) (3f) the NMR data show that only the complex with the C(Me)N moiety of the ligand σ-N coordinated to the Ru atom and the C(H)N moiety η²-coordinated to the Fe atom was formed. Variable temperature NMR experiments up to 140 °C showed that the α-diimine ligand in 3a is stereochemically rigid bonded.FeRu(CO)₆(R-DAB(6e)) (3a and 3e) reacted with allene to give FeRu(CO)₅(R-DAB(4e))(C₃H₄) (4a and 4e). A single crystal X-ray structure determination of FeRu(CO)₅(i-Pr-DAB(4e))(C₃H₄) (4a) was performed. Crystals of 4a are triclinic, space group P1, with two molecules in a unit cell of dimensions: a = 9.7882(7), b = 12.2609(9), c = 8.3343(7) Å, α = 99.77(1)°, β = 91.47(1)° and γ = 86.00(1)°. The structure was refined to R = 0.028 and R_w = 0.043 using 4598 reflections above the 2σ(I) level. The molecule contains an FeRu bond of 2.7405(7) Å and three terminally bonded carbonyls to iron. Two carbonyls are terminally bonded to the Ru atom together with a chelating 4e donating i-Pr-DAB ligand [RuN = 2.110(1) (mean)]. The allene ligand is coordinated in an η³-allylic fashion to the Fe atom while the central carbon of the allene moiety is σ-bonded to the Ru atom (FeC(14) = 2.166(3), FeC(15) = 1.970(2), FeC(16) = 2.127(3) and RuC(15) = 2.075(2) Å). The ¹H and ¹³C NMR data show that in solution the coordination modes of the R-DAB and the allene ligands are the same as in the solid state.Thermolysis reactions of 3a with R-DAB or carbodiimides gave decomposition and did not afford C(imine)C(reactant) coupling products. Thermolysis reactions of 3a with M₃(CO)₁₂ (M = Ru, Os) and Me₃NO gave decomposition. When the reaction of 3a with Me₃NO was performed in the presence of dimethylacetylenedicarboxylate (DMADC) the known complex FeRu(CO)₄(i-Pr-DAB(8e))(DMADC) (5a) was formed in low yield. In 5a the R-DAB ligand is in the 8e coordination mode with both the imine bonds η²-coordinated to iron. The acetylene ligand is coordinated in a bridging fashion, parallel with the FeRu bond.