Molecular dynamics simulations reveal highly permeable oxygen exit channels shared with water uptake channels in photosystem II.

Photosystem II (PSII) catalyzes the oxidation of water in the conversion of light energy into chemical energy in photosynthesis. Water delivery and oxygen removal from the oxygen evolving complex (OEC), buried deep within PSII, are critical requirements to facilitate the reaction and minimize reactive oxygen damage. It has often been assumed that water and oxygen travel through separate channels within PSII, as demonstrated in cytochrome c oxidase. This study describes all-atom molecular dynamics simulations of PSII designed to investigate channels by fully characterizing the distribution and permeation of both water and oxygen. Interestingly, most channels found in PSII were permeable to both oxygen and water, however individual channels exhibited different energetic barriers for the two solutes. Several routes for oxygen diffusion within PSII with low energy permeation barriers were found, ensuring its fast removal from the OEC. In contrast, all routes for water showed significant energy barriers, corresponding to a much slower permeation rate for water through PSII. Two major factors were responsible for this selectivity: (1) hydrogen bonds between water and channel amino acids, and (2) steric restraints. Our results reveal the presence of a shared network of channels in PSII optimized to both facilitate the quick removal of oxygen and effectively restrict the water supply to the OEC to help stabilize and protect it from small water soluble inhibitors.

Exploring the energetics of water permeation in photosystem II by multiple steered molecular dynamics simulations.

The Mn(4)Ca cluster of the oxygen-evolving complex (OEC) of photosynthesis catalyzes the light-driven splitting of water into molecular oxygen, protons, and electrons. The OEC is buried within photosystem II (PSII), a multisubunit integral membrane protein complex, and water must find its way to the Mn(4)Ca cluster by moving through protein. Molecular dynamics simulations were used to determine the energetic barriers for water permeation though PSII extrinsic proteins. Potentials of mean force (PMFs) for water were derived by using the technique of multiple steered molecular dynamics (MSMD). Calculation of free energy profiles for water permeation allowed us to characterize previously identified water channels, and discover new pathways for water movement toward the Mn(4)Ca cluster. Our results identify the main constriction sites in these pathways which may serve as selectivity filters that restrict both the access of solutes detrimental to the water oxidation reaction and loss of Ca(2+) and Cl(-) from the active site.

Diffusion tensor imaging in evaluation of human skeletal muscle injury.

PURPOSE: To explore the capability and reliability of diffusion tensor magnetic resonance imaging (DTI) in the evaluation of human skeletal muscle injury. MATERIALS AND METHODS: DTI of four patients with gastrocnemius and soleus muscles injuries was compared to eight healthy controls. Imaging was performed using a GE 3.0T short-bore scanner. A diffusion-weighted 2D spin echo echo-planar imaging (EPI) pulse sequence optimized for skeletal muscle was used. From a series of axially acquired diffusion tensor images the diffusion tensor eigenparameters (eigenvalues and eigenvectors), fractional anisotropy (FA), and apparent diffusion coefficient (ADC) were calculated and compared for injured and healthy calf muscles. Two dimensional (2D) projection maps of the principal eigenvectors were plotted to visualize the healthy and pathologic muscle fiber architectures. RESULTS: Clear differences in FA and ADC were observed in injured skeletal muscle, compared to healthy controls. Mean control FA was 0.23 +/- 0.02 for medial and lateral gastrocnemius (mg and lg) muscles, and 0.20 +/- 0.02 for soleus (sol) muscles. In all patients FA values were reduced compared to controls, to as low as 0.08 +/- 0.02. The ADC in controls ranged from 1.41 to 1.31 x 10(-9) m(2)/second, while in patients this was consistently higher. The 2D projection maps revealed muscle fiber disorder in injured calves, while in healthy controls the 2D projection maps show a well organized (ordered) fiber structure. CONCLUSION: DTI is a suitable method to assess human calf muscle injury.

Changes in molecular order across the lamellar-to-inverted hexagonal phase transition depend on the position of the double-bond in mono-unsaturated phospholipid dispersions.

A series of mono-unsaturated phosphatidylethanolamine (PE) model membranes is studied using deuterium nuclear magnetic resonance (NMR) and differential scanning calorimetry. As the position of the double bond is systematically changed, the internal conformational motions are monitored through the bilayer-to-inverted-hexagonal phase transition. The order parameter profiles extracted from the NMR spectra report on the conformational order of the lipid and on the way this order is changed by structural reorganizations of the membrane. The calculation of a ratio of renormalized order parameter profiles is presented here as an attempt to distill the essential features of these changes into dimensionless descriptions of "shape" functions. This variation of the extent of molecular disorder along the long molecular axis of the phospholipids appears to be a recurring motif, modulated by temperature, structural rearrangement, and chemical composition of the membrane. The reported experimentally measured changes in the shape of the order parameter profile can be compared to those obtained during molecular dynamics simulation studies.