Freezing temperature effects on photosystem II in Antarctic lichens evaluated by chlorophyll fluorescence.

This study explores and compares the limits for photosynthesis in subzero temperatures of six Antarctic lichens: Sphaerophorus globosus, Caloplaca regalis, Umbilicaria antarctica, Pseudephebe minuscula, Parmelia saxatilis and Lecania brialmontii combining linear cooling and chlorophyll fluorescence methods. The results revealed triphasic S-curves in the temperature response of the maximum quantum yield (FV/FM) and effective quantum yield of photosystem II (ΦPSII) for all species. All investigated species showed a high level of cryoresistance with critical temperatures (Tc) below -20 °C. However, record low Tc temperatures have been discovered for L. brialmotii (-54 °C for FV/FM and -40 °C for ΦPSII) and C. regalis (-52 °C for FV/FM and -38 °C for ΦPSII). Additionally, the yield differentials (FV/FM - ΦPSII) in functions of temperature revealed one or two peaks, with the larger one occurring for temperatures below -20 °C for the above-mentioned species. Finally, Kautsky kinetics were measured and compared at different temperatures (20 °C, 10 °C, 0 °C and -10 °C and then -10 °C after 1 h of incubation). This research serves as a foundation for further developing investigations into the biophysical mechanisms by which photosynthesis is carried out at subzero temperatures.

Revealing a Third Dissolved-Phase Xenon-129 Resonance in Blood Caused by Hemoglobin Glycation.

Hyperpolarized (HP) xenon-129 (129Xe), when dissolved in blood, has two NMR resonances: one in red blood cells (RBC) and one in plasma. The impact of numerous blood components on these resonances, however, has not yet been investigated. This study evaluates the effects of elevated glucose levels on the chemical shift (CS) and T2* relaxation times of HP 129Xe dissolved in sterile citrated sheep blood for the first time. HP 129Xe was mixed with sheep blood samples premixed with a stock glucose solution using a liquid-gas exchange module. Magnetic resonance spectroscopy was performed on a 3T clinical MRI scanner using a custom-built quadrature dual-tuned 129Xe/1H coil. We observed an additional resonance for the RBCs (129Xe-RBC1) for the increased glucose levels. The CS of 129Xe-RBC1 and 129Xe-plasma peaks did not change with glucose levels, while the CS of 129Xe-RBC2 (original RBC resonance) increased linearly at a rate of 0.015 ± 0.002 ppm/mM with glucose level. 129Xe-RBC1 T2* values increased nonlinearly from 1.58 ± 0.24 ms to 2.67 ± 0.40 ms. As a result of the increased glucose levels in blood samples, the novel additional HP 129Xe dissolved phase resonance was observed in blood and attributed to the 129Xe bound to glycated hemoglobin (HbA1c).

Data regarding particle size distribution, thermal properties and gaseous phase hydration of co-milled solid dispersions composed of tadalafil and Soluplus.

A mechanical activation of the solid particles upon high-energy ball milling may considerably change the physicochemical properties of pharmaceutical compounds, including the morphology, particle size distribution, thermal properties, and surface interactions with water vapour upon gaseous phase hydration. Assessment of these changes is crucial for optimizing the manufacturing process of enabling drug products. In this article, we provide a detailed characterization of binary co-milled solid dispersions composed of tadalafil and Soluplus using a laser diffraction method, differential scanning calorimetry (DSC), gravimetric measurements and solid state 1H- NMR spectroscopy. The data presented in this article is directly related to our previously published research article. They complement information on the impact that both formulation and process variables may have on the properties of these binary powder formulations.

Rehydration of the sleeping chironomid, Polypedilum vanderplanki Hinton, 1951 larvae from cryptobiotic state up to full physiological hydration (Diptera: Chironomidae).

During desiccation the Polypedilum vanderplanki larva loses 97% of its body water, resulting in the shutdown of all metabolic and physiological processes. The larvae are able to resume active life when rehydrated. As dehydration process has already been largely understood, rehydration mechanisms are still poorly recognized. X-ray microtomograms and electron scanning microscopy images recorded during the hydration showed that the volume of the larva's head hardly changes, while the remaining parts of the body increase in volume. In the 1H-NMR spectrum, as recorded for active larvae, component characteristic of solid state matter is absent. The spectrum is superposition of components coming from tightly and loosely bound water fraction, as well as from lipids. The value of the c coefficient (0.66 ± 0.02) of the allometric function describing the hydration models means that the increase in the volume of rehydrated larvae over time is linear. The initial phase of hydration does not depend on the chemical composition of water, but the amount of ions affects the further process and the rate of return of larva's to active life. Diffusion and ion channels play a major role in the permeability of water through the larva's body integument.

A comparative analysis of gaseous phase hydration properties of two lichenized fungi: Niebla tigrina (Follman) Rundel & Bowler from Atacama Desert and Umbilicaria antarctica Frey & I. M. Lamb from Robert Island, Southern Shetlands Archipelago, maritime Antarctica.

Gaseous phase hydration properties for thalli of Niebla tigrina from Atacama Desert, and for Umbilicaria antarctica from Isla Robert, maritime Antarctica, were analyzed using 1H-NMR relaxometry, spectroscopy, and sorption isotherm analysis. The molecular dynamics of residual water was monitored to distinguish the sequential binding very tightly, tightly, and loosely bound water fractions. These two species differ in hydration kinetics faster for Desert N. tigrina [A1 = 0.51(4); t1 = 0.51(5) h, t2 = 15.0(1.9) h; total 0.7 for p/p0 = 100%], compared to Antarctic U. antarctica [A1 = 0.082(6), t1 = 2.4(2) h, t2 = [26.9(2.7)] h, total 0.6 for p/p0 = 100%] from humid polar area. The 1H-NMR measurements distinguish signal from tightly bound water, and two signals from loosely bound water, with different chemical shifts higher for U. antarctica than for N. tigrina. Both lichen species contain different amounts of water-soluble solid fraction. For U. antarctica, the saturation concentration of water soluble solid fraction, cs = 0.55(9), and the dissolution effect is detected at least up to Δm/m0 = 0.7, whereas for N. tigrina with the similar saturation concentration, cs = 053(4), this fraction is detected up to the threshold hydration level equal to ΔM/m0 = 0.3 only.

Non-cooperative immobilization of residual water bound in lyophilized photosynthetic lamellae.

This study applied 1H-NMR in time and in frequency domain measurements to monitor the changes that occur in bound water dynamics at decreased temperature and with increased hydration level in lyophilizates of native wheat photosynthetic lamellae and in photosynthetic lamellae reconstituted from lyophilizate. Proton relaxometry (measured as free induction decay = FID) distinguishes a Gaussian component S within the NMR signal (o). This comes from protons of the solid matrix of the lamellae and consists of (i) an exponentially decaying contribution L1 from mobile membrane protons, presumably from lipids, and from water that is tightly bound to the membrane surface and thus restricted in mobility; and (ii) an exponentially decaying component L2 from more mobile, loosely bound water pool. Both proton relaxometry data and proton spectroscopy show that dry lyophilizate incubated in dry air, i.e., at a relative humidity (p/p0) of 0% reveals a relatively high hydration level. The observed liquid signal most likely originates from mobile membrane protons and a tightly bound water fraction that is sealed in pores of dry lyophilizate and thus restricted in mobility. The estimations suggest that the amount of sealed water does not exceed the value characteristic for the main hydration shell of a phospholipid. Proton spectra collected for dry lyophilizate of photosynthetic lamellae show a continuous decrease in the liquid signal component without a distinct freezing transition when it is cooled down to -60ºC, which is significantly lower than the homogeneous ice nucleation temperature [Bronshteyn, V.L. et al. Biophys. J. 65 (1993) 1853].

Vibrations and reorientations of H2O molecules in [Sr(H2O)6]Cl2 studied by Raman light scattering, incoherent inelastic neutron scattering and proton magnetic resonance.

Vibrational-reorientational dynamics of H2O ligands in the high- and low-temperature phases of [Sr(H2O)6]Cl2 was investigated by Raman Spectroscopy (RS), proton magnetic resonance ((1)H NMR), quasielastic and inelastic incoherent Neutron Scattering (QENS and IINS) methods. Neutron powder diffraction (NPD) measurements, performed simultaneously with QENS, did not indicated a change of the crystal structure at the phase transition (detected earlier by differential scanning calorimetry (DSC) at TC(h)=252.9 K (on heating) and at TC(c)=226.5K (on cooling)). Temperature dependence of the full-width at half-maximum (FWHM) of νs(OH) band at ca. 3248 cm(-1) in the RS spectra indicated small discontinuity in the vicinity of phase transition temperature, what suggests that the observed phase transition may be associated with a change of the H2O reorientational dynamics. However, an activation energy value (Ea) for the reorientational motions of H2O ligands in both phases is nearly the same and equals to ca. 8 kJ mol(-1). The QENS peaks, registered for low temperature phase do not show any broadening. However, in the high temperature phase a small QENS broadening is clearly visible, what implies that the reorientational dynamics of H2O ligands undergoes a change at the phase transition. (1)H NMR line is a superposition of two powder Pake doublets, differentiated by a dipolar broadening, suggesting that there are two types of the water molecules in the crystal lattice of [Sr(H2O)6]Cl2 which are structurally not equivalent average distances between the interacting protons are: 1.39 and 1.18 Å. However, their reorientational dynamics is very similar (τc=3.3⋅10(-10) s). Activation energies for the reorientational motion of these both kinds of H2O ligands have nearly the same values in an experimental error limit: and equal to ca. 40 kJ mole(-1). The phase transition is not seen in the (1)H NMR spectra temperature dependencies. Infrared (IR), Raman (RS) and inelastic incoherent neutron scattering (IINS) spectra were calculated by the DFT method and quite a good agreement with the experimental data was obtained.