The Mn cluster in the S(0) state of the oxygen-evolving complex of photosystem II studied by EXAFS spectroscopy: are there three Di-mu-oxo-bridged Mn(2) moieties in the tetranuclear Mn complex?

A key component required for an understanding of the mechanism of the evolution of molecular oxygen by the photosynthetic oxygen-evolving complex (OEC) in photosystem II (PS II) is the knowledge of the structures of the Mn cluster in the OEC in each of its intermediate redox states, or S-states. In this paper, we report the first detailed structural characterization using Mn extended X-ray absorption fine structure (EXAFS) spectroscopy of the Mn cluster of the OEC in the S(0) state, which exists immediately after the release of molecular oxygen. On the basis of the EXAFS spectroscopic results, the most likely interpretation is that one of the di-mu-oxo-bridged Mn-Mn moieties in the OEC has increased in distance from 2.7 A in the dark-stable S(1) state to 2.85 A in the S(0) state. Furthermore, curve fitting of the distance heterogeneity present in the EXAFS data from the S(0) state leads to the intriguing possibility that three di-mu-oxo-bridged Mn-Mn moieties may exist in the OEC instead of the two di-mu-oxo-bridged Mn-Mn moieties that are widely used in proposed structural models for the OEC. This possibility is developed using novel structural models for the Mn cluster in the OEC which are consistent with the structural information available from EXAFS and the recent X-ray crystallographic structure of PS II at 3.8 A resolution.     

Excess molar volumes of methylcyclohexane+benzene, +methylbenzene, +1,4-dioxane,and +tetrahydrofuran at 303.15 K

Excess molar volumes V_m^E as function of mole fraction x for methylcyclohexane + benzene, + methylbenzene, + 1,4-dioxane, and + tetrahydrofuran are reported at 303.15 K. The excess molar volumes are positive and indicate the presence of weak interactions.     

A novel liquid chromatography/tandem mass spectrometry based depletion method for measuring red blood cell partitioning of pharmaceutical compounds in drug discovery

A novel liquid chromatography/tandem mass spectrometry (LC/MS/MS)-based depletion method for measuring compound partitioning between human plasma and red blood cells (RBC) in a drug discovery environment is presented. Conventionally, RBC partitioning is determined by separate measurements of drug concentrations in equilibrating plasma and whole blood or RBC using separate standards prepared in their respective matrices, i.e., in plasma and whole blood or RBC lysates. The process is very tedious, labor-intensive, and difficult to automate. In addition, interferences from the heme and other highly abundant cellular composites make the measurement of the drug concentration in whole blood or RBC inevitably variable even with a highly specific LC/MS/MS method. Therefore, there is an imminent need to develop a straightforward and fast method to assess the partitioning of drug-like compounds in RBC.This work describes an LC/MS/MS-based depletion assay that measures the compound concentration in plasma that has been equilibrating with RBC. Compounds were spiked into fresh human whole blood and plasma respectively to a final concentration of 500 nM. Both the spiked whole blood and plasma control were incubated at 37 degrees C for up to 60 min. During the time course, aliquots of plasma and whole blood from both incubation mixtures were sampled at 10 and 60 min. The whole blood samples were centrifuged to yield the plasma. The plasma samples from both incubations were extracted using a protein precipitation method, and analyzed using LC/MS/MS under the multiple-reaction monitoring (MRM) mode. The RBC partitioning ratio was calculated using the analyte peak area responses of the plasma samples through an equation deduced in this work.The method was first tested using two commercial compounds, phenoprobamate and acetazolamide, to determine the optimal incubation conditions and the concentration dependency of the assay. The assay reproducibility was also assessed by three inter-day assays for phenoprobamate. This method was further evaluated using 20 commercial compounds of different classes with a wide range of RBC partitioning coefficients and the results were compared with those reported in the literature. Excellent correlation (R2=0.9396) was found between the measured and literature values. In addition, several proprietary compounds were assayed using both the new and traditional methods and the measured partitioning ratios from the two methods are equivalent. The experiments in this work demonstrate that the LC/MS/MS-based depletion method can provide direct and accurate measurement of RBC partitioning for compounds in drug discovery.     

The discrete fundamental group of the order complex of <Emphasis Type="Italic">B</Emphasis><Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

A few years ago Kramer and Laubenbacher introduced a discrete notion of homotopy for simplicial complexes. In this paper, we compute the discrete fundamental group of the order complex of the Boolean lattice. As it turns out, it is equivalent to computing the discrete homotopy group of the 1-skeleton of the permutahedron. To compute this group we introduce combinatorial techniques that we believe will be helpful in computing discrete fundamental groups of other polytopes. More precisely, we use the language of words, over the alphabet of simple transpositions, to obtain conditions that are necessary and sufficient to characterize the equivalence classes of cycles. The proof requires only simple combinatorial arguments. As a corollary, we also obtain a combinatorial proof of the fact that the first Betti number of the complement of the 3-equal arrangement is equal to 2 ^n?3(n ²?5n+8)?1. This formula was originally obtained by Björner and Welker in 1995.     

Dosimetry of Room-Air Germicidal (254 nm) Radiation Using Spherical Actinometry

A method is demonstrated for measuring germicidal (254 nm) ultraviolet radiation (GUVR) in an omnidirectional manner. This method has application for those situations in which GUVR from more than one direction or source impinges on a three-dimensional object, and when it is of interest to determine the radiant fluence experienced by the object. For this purpose spherical quartz vessels were constructed varying from 0.8 to 1.25 cm in outside diameter. The vessels were filled with an actinometric solution consisting of KI and KIO3. This solution is optically opaque at 254 nm and is insensitive to room light. Upon exposure to GUVR this solution, which counts all of the 254 nm photons, forms triiodide. Following radiation, the contents of the vessel are removed, the absorbance of triiodide measured and the fluence rate determined based on a relationship that takes the volume to cross-sectional area of the actinometer into account. It is demonstrated that, in accordance with theory, the area of the sphere that intercepts the radiant energy is equal to the cross-sectional area of the sphere. A demonstration of the utility of this method was carried out in a test facility 90 m3 equipped with five GUVR lamps, one in each corner and one in the center of the room, arranged so as to irradiate the air in the upper portion of the room. Twenty spherical actinometers were evenly distributed around the room and exposed for either 30 or 90 min. The fluence rate varied from one part of the room to another, peaking near the GUVR lamps at 65-85 microW per cm2. By averaging over all 20 points, a pseudoaverage fluence rate for the room was found to be 42 and 44 microW per cm2 for the 30 and 90 min exposures, respectively. The similarities in the values for this metric demonstrates that the actinometric response is linear over this exposure range.     

Oxidation of electron deficient olefins using a copper(II) complex based on a bis-benzimidazole diamide ligand

New bis-benzimidazole based diamide ligands N, N′-bis(2-methyl benzimidazolyl)-benzene-1,3-dicarboxamide [GBBA] and N-Octyl-N, N′-bis(2-methyl benzimidazolyl)-benzene- 1,3-dicarboxamide [O-GBBA] have been synthesized and utilized to prepare Cu(II) complexes of general composition [Cu(GBBA)X ₂] · nH₂O and [Cu(O-GBBA)X₂] · n H₂O, where X is an exogenous anionic ligand (X = Cl⁻, NO₃⁻, SCN⁻). The oxidation of electron deficient olefins has been investigated using [Cu(O-GBBA)X₂] · nH₂O as catalyst and TBHP as an alternate source of oxygen. The respective ketonic products have been isolated and characterized by ¹H-NMR. The complex [Cu(GBBA)(NO₃)₂] · 4H₂O has been characterized structurally. It crystallizes in a monoclinic space group C2/c. Low temperature EPR spectra have been obtained for the complexes that shows g_II > g_I > 2.0024, indicating a tetragonal geometry in the solution state. The complexes display a quasi reversible redox wave due to the Cu(II)/Cu(I) reduction process. The E_1/2 values shift anodically as NO₃⁻ < SCN⁻ < Cl⁻.     

Volumetric and Ultrasonic Studies on Interactions of Hexylene and Propylene Glycols in Aqueous Solutions of Glutaraldehyde at Different Temperatures

Journal of Solution Chemistry - To determine the various interactions between glutaraldehyde and glycols (hexylene and propylene), various thermodynamic and acoustic properties have been analysed...     

Multi-element analysis of soil from the north-western region of India by neutron activation analysis using the single comparator method with special reference to selenium toxicity

The single comparator (k₀) instrumental neutron activation analysis (INAA) was employed to determine the elemental composition of soil from the north-western region of India. The radiometric assay was carried out using high resolution gamma-ray spectrometry. Seventeen elements were detected including selenium whose concentration was found to be in the range of 1.02 to 6.79 mg/g.