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Wildfire is the main disturbance in most boreal forests. In the prolonged absence of wildfire, ecosystem retrogression occurs, which is characterized by reduced productivity, plant biomass and belowground process rates. Previous evidence suggests that phosphorus (P) decreases during retrogression, but the mechanisms involved remain poorly understood. Here we use 1-D ³¹P and 2-D, ¹H-³¹P NMR to characterize changes in humus P composition across a 5000 year post-fire chronosequence in northern Sweden, to understand why P availability declines during long term fire absence. Against expectations, humus P composition varied only modestly with increasing time since fire. Using a method to back-calculate the in situ soil organic P speciation, we found that it was dominated by biologically active compounds such as RNA (41%), phospholipids (28%) and DNA (22%). The concentration of DNA and pyrophosphate was 19% and 29% lower, respectively, on infrequently burnt than recently burnt islands, and the concentration of DNA, phospholipids and nucleotides was positively correlated with net primary productivity (NPP). Given the lack of evidence for the accumulation of “recalcitrant” P or a geochemical P sink, reductions in P availability during retrogression may be associated with impaired P cycling through slower decomposition rates, and increasing humus depth separating surface humus from P-rich mineral soil. Our findings align with observed negative relationships between NPP and organic P concentration across other chronosequences. They also suggest that changing fire regimes in the boreal zone could indirectly affect the P cycle through changes in NPP and soil microflora rather than through changes in humus P composition.

Organic phosphorus (P) is an important component of boreal forest humus soils, and its concentration has been found to be closely related to the concentration of iron (Fe) and aluminium (Al). We used solution and solid state 31P NMR spectroscopy on humus soils to characterize organic P along two groundwater recharge and discharge gradients in Fennoscandian boreal forest, which are also P sorption gradients due to differences in aluminium (Al) and iron (Fe) concentration in the humus. The composition of organic P changed sharply along the gradients. Phosphate diesters and their degradation products, as well as polyphosphates, were proportionally more abundant in low Al and Fe sites, whereas phosphate monoesters such as myo-, scyllo- and unknown inositol phosphates dominated in high Al and Fe soils. The concentration of inositol phosphates, but not that of diesters, was positively related to Al and Fe concentration in the humus soil. Overall, in high Al and Fe sites the composition of organic P seemed to be closely associated with stabilization processes, whereas in low Al and Fe sites it more closely reflected inputs of organic P, given the dominance of diesters which are generally assumed to constitute the bulk of organic P inputs to the soil. These gradients encompass the broad variation in soil properties detected in the wider Fennoscandian boreal forest landscape, as such our findings provide insight into the factors controlling P biogeochemistry in the region but should be of relevance to boreal forests elsewhere.

Background and Aims Soil phosphorus (P) composition changes with ecosystem development, leading to changes in P bioavailability and ecosystem properties. Little is known, however, about how soil P transformations proceed with ecosystem development in boreal regions. Methods We used 1-dimensional ³¹P and 2-dimensional ¹H, ³¹P correlation nuclear magnetic resonance (NMR) spectroscopy to characterise soil organic P transformations in humus horizons across a 7,800 year-old chronosequence in Västerbotten, northern Sweden. Results Total soil P concentration varied little along the chronosequence, but P compounds followed three trends. Firstly, the concentrations of DNA, 2-aminoethyl phosphonic acid, and polyphosphate, increased up to 1,200-2,700 years and then declined. Secondly, the abundances of α-and β—glycerophosphate, nucleotides, and pyrophosphate, were higher at the youngest site compared with all other sites. Lastly, concentrations of inositol hexakisphosphate fluctuated with site age. The largest changes in soil P composition tended to occur in young sites which also experience the largest shifts in plant community composition. Conclusions The apparent lack of change in total soil P is consistent with the youth and nitrogen limited nature of the Västerbotten chronosequence. Based on 2D NMR spectra, around 40 % of extractable soil organic P appeared to occur in live microbial cells. The observed trends in soil organic P may be related to shifts in plant community composition (and associated changes in soil microorganisms) along the studied chronosequence, but further studies are needed to confirm this.

In this paper, we presented new J-oriented basis sets, pecJ-n (n = 1, 2), for phosphorus and silicon, purposed for the high-quality correlated calculations of the NMR spin–spin coupling constants involving these nuclei. The pecJ-n basis sets were generated using the modified version of the property-energy consistent (PEC) method, which was introduced in our earlier paper. The modifications applied to the original PEC procedure increased the overall accuracy and robustness of the generated basis sets in relation to the diversity of electronic systems. Our new basis sets were successfully tested on a great number of spin–spin coupling constants, involving phosphorus or/and silicon, calculated within the SOPPA(CCSD) method. In general, it was found that our new pecJ-1 and pecJ-2 basis sets are very efficient, providing the overall accuracy that can be characterized by MAEs of about 3.80 and 1.98 Hz, respectively, against the benchmark data obtained with a large dyall.aae4z+ basis set of quadruple-ζ quality.

Soil phosphorus (P), which is essential for ecosystem functioning, undergoes notable changes after fire. However, the extent to which fire characteristics affect P dynamics remains largely unknown. This study investigated the impact of type of fire (prescribed burning and natural wildfires) of different levels of severity on P dynamics in Mediterranean soils. Soil P concentrations in the organic layers were strongly affected by fire severity but not fire type. Low severity fire did not have any observable effect, while moderate fire increased soil P levels by 62% and high severity decreased soil P concentration by 19%. After one year, the soil P concentration remained unchanged in the low severity fires, while rather complex recovery was observed after moderate and high severity fires. In the mineral layers, P concentration was reduced (by 25%) immediately after the fires and maintained for one year (at 42%). 31 P-NMR spectroscopy revealed almost complete post-fire mineralization of organic P forms (mono- and diesters), large increases in inorganic orthophosphate and a decrease in the organic:inorganic P ratio ( P o :P i ). After one year, di-esters and orthophosphate recovered to pre-fire levels at all sites, except those where parent material composition (high pH and Fe concentration) had an enduring effect on orthophosphate retention, and thus, on the total soil P. We showed that fire severity and soil pH (and hence, soil mineralogy) played an essential role in soil P dynamics. These findings are important for reliable assessment of the effects of fire on soil P conservation and for improving the understanding the impact of prescribed burning.

In animal and plant cells, the ATP/ADP ratio and/or energy charge are generally considered key parameters regulating metabolism and respiration. The major alternative issue of whether the cytosolic and mitochondrial concentrations of ADP and ATP directly mediate cell respiration remains unclear, however. In addition, because only free nucleotides are exchanged by the mitochondrial ADP/ATP carrier, whereas MgADP is the substrate of ATP synthase (EC 3.6.3.14), the cytosolic and mitochondrial Mg2+ concentrations must be considered as well. Here we developed in vivo/in vitro techniques using P-31-NMR spectroscopy to simultaneously measure these key components in subcellular compartments. We show that heterotrophic sycamore (Acer pseudoplatanus L.) cells incubated in various nutrient media contain low, stable cytosolic ADP and Mg2+ concentrations, unlike ATP. ADP is mainly free in the cytosol, but complexed by Mg2+ in the mitochondrial matrix, where [Mg2+] is tenfold higher. In contrast, owing to a much higher affinity for Mg2+, ATP is mostly complexed by Mg2+ in both compartments. Mg2+ starvation used to alter cytosolic and mitochondrial [Mg2+] reversibly increases free nucleotide concentration in the cytosol and matrix, enhances ADP at the expense of ATP, decreases coupled respiration, and stops cell growth. We conclude that the cytosolic ADP concentration, and not ATP, ATP/ADP ratio, or energy charge, controls the respiration of plant cells. The Mg2+ concentration, remarkably constant and low in the cytosol and tenfold higher in the matrix, mediates ADP/ATP exchange between the cytosol and matrix, [MgADP]-dependent mitochondrial ATP synthase activity, and cytosolic free ADP homeostasis.

An extensive series of 128 halogen-bonded complexes formed by trimethylphosphine oxide and various F-, Cl-, Br-, I- and At-containing molecules, ranging in energy from 0 to 124 kJ/mol, is studied by DFT calculations in vacuum. The results reveal correlations between R–X⋅⋅⋅O=PMe3 halogen bond energy ΔE, X⋅⋅⋅O distance r, halogen’s σ-hole size, QTAIM parameters at halogen bond critical point and changes of spectroscopic parameters of phosphine oxide upon complexation, such as 31P NMR chemical shift, ΔδP, and P=O stretching frequency, Δν. Some of the correlations are halogen-specific, i.e., different for F, Cl, Br, I and At, such as ΔE(r), while others are general, i.e., fulfilled for the whole set of complexes at once, such as ΔE(ΔδP). The proposed correlations could be used to estimate the halogen bond properties in disordered media (liquids, solutions, polymers, glasses) from the corresponding NMR and IR spectra.

Dendrimers, being highly branched monodispersed macromolecules, predominantly exhibit identical terminal functionalities within their structural framework. Nonetheless, there are instances where the presence of two distinct surface functionalities becomes advantageous for the fulfilment of specific properties. To achieve this objective, one approach involves implementing Janus dendrimers, consisting of two dendrimeric wedges terminated by dissimilar functionalities. The prevalent method for creating these structures involves the synthesis of dendrons that possess a core functionality that complements that of a second dendron, facilitating their coupling to generate the desired dendrimers. In this comprehensive review, various techniques employed in the fabrication of phosphorus-based Janus dendrimers are elucidated, displaying the different coupling methodologies employed between the two units. The advantages of phosphorus dendrimers over classic dendrimers will be shown, as the presence of at least one phosphorus atom in each generation allows for the easy monitoring of reactions and the confirmation of purity through a simple technique such as 31P NMR, as these structures typically exhibit easily interpretable patterns.

To understand the bilayer interaction with paclitaxel, fluorescence polarization, Fourier transform infrared spectroscopy (FT-IR) and 31-phosphorus nuclear magnetic resonance (31P-NMR) studies were performed on paclitaxel bearing liposomes. Fluorescence anisotropy of three probes namely, 1,6-diphenyl-1,3,5-hexatriene (DPH), 12-(9-anthroyloxy) stearic acid (12AS) and 8-anilino-1-naphthalene sulfonate (ANS) were monitored as a function of paclitaxel concentration in the unsaturated bilayers. The incorporation of paclitaxel decreased anisotropy of 12AS and ANS probes, while slightly increased anisotropy of DPH. Paclitaxel has a fluidizing effect in the upper region of the bilayer whereas the hydrophobic core is slightly rigidized. FT-IR spectroscopy showed an increase in the asymmetric and symmetric methylene stretching frequencies, splitting of methylene scissoring band and broadening of carbonyl stretching mode. These studies collectively ascertained that paclitaxel mainly occupies the cooperativity region and interact with the interfacial region of unsaturated bilayers and induces fluidity in the headgroup region of bilayer. At higher loadings (>3 mol%), paclitaxel might gradually tend to accumulate at the interface and eventually partition out of bilayer as a result of solute exclusion phenomenon, resulting in crystallization; seed non-bilayer phases, as revealed by 31P-NMR, thereby destabilizing liposomal formulations. In general, any membrane component which has a rigidization effect will decrease, while that with a fluidizing effect will increase, with a bearing on headgroup interactions, partitioning of paclitaxel into bilayers and stability of the liposomes.

The hypoxic microenvironment is crucial for tumour cell growth and invasiveness. Tumour tissue results from adaptation to reduced oxygen availability. Hypoxia first activates pro‐angiogenic signals for alleviation. Pathologic, tumour angiogenesis maintains hypoxia, impairing treatment outcomes. Vessel normalisation requires physioxia. Oxygen delivery by red blood cell (RBC) carrying haemoglobin (Hb) is enhanced by myo‐inositol trispyrophosphate (ITPP), an effector of oxygen transport by RBCs. Altering glycolytic activity, it lowers intracellular pH and increases oxygen release from Hb. 31P NMR tracking of 2,3‐diphosphoglycerate (2,3‐DPG), allosteric effector of Hb and non‐penetrating anion in RBCs, reports on erythrocytes internal environment. 31P resonances of 2,3‐DPG are pH‐sensitive, their positions indicate the oxygenation state of RBCs and interactions with effectors such as ITPP. Here we show in vitro and in vivo, that modifying Hb activity through band‐3 anion transporter, ITPP enhances oxygen release and controls RBC internal pH. Its blood availability validates applicability of ITPP‐based strategies.