Highly Proton-Conductive Zinc Metal-Organic Framework Based On Nickel(II) Porphyrinylphosphonate

The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10⁻³ S cm⁻¹ at 75 °C and 80 % relative humidity).     

Stability of O3 + N2, O3 + O2 and O3 + CO2 double hydrates: DFT study

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Statistical Inference with Fractional Brownian Motion

We give a test between two complex hypothesis; namely we test whether a fractional Brownian motion (fBm) has a linear trend against a certain non-linear trend. We study some related questions, like goodness-of-fit test and volatility estimation in these models.     

Intramolecular heterocyclization with accompanying exoiminization in the reaction of ammonia with 2-chloroperfluoro-1-cyclohexene-1-thiocyanate

The reaction of ammonia with 2-chloroperfluoro-1-cyclohexene-1-thiocyanate leads to 2-amino-7-iminoperfluoro-4,5,6-trihydrobenzo-1,3-thiazole (II) due to intramolecular heterocyclization in the Thorpe reaction with the concurrent exoiminization. Analysis of the IR spectra of (II) in CCl₄ and in the solid phase indicated that molecules of (II) in the crystal form hydrogen-bonded centrosymmetric dimers (D), which are in equilibrium with free molecules of (II) in solution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2366–2370, October, 1991.The authors express their gratitude to D. I. Zagorevskii for taking the mass spectrum of (II) and to L. S. German for a useful discussion of this work.     

Fluorine-containing α-hydrothionyl fluorides

A method has been found for the synthesis of fluoride-containing -hydrothionyl fluorides by heating polyfluoroalkenyl benzyl sulfides having fluoride atoms in the -position relative to the sulfur atom with fluorosulfonic acid. The reactions of the acid fluorides obtained with secondary amines were studied. The reaction of the -hydrotetrafluorothiopropionyl fluoride with NH(Me)₂ leads to the amide of the corresponding acid, while the product of -hydrohexafluorothioisobutyryl fluoride with diethylamine is the dimer of bis(trifluoromethyl)thioketene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1898–1901, August, 1990.     

Fast 3D shape screening of large chemical databases through alignment-recycling

Background  

Large chemical databases require fast, efficient, and simple ways of looking for similar structures. Although such tasks are now fairly well resolved for graph-based similarity queries, they remain an issue for 3D approaches, particularly for those based on 3D shape overlays. Inspired by a recent technique developed to compare molecular shapes, we designed a hybrid methodology, alignment-recycling, that enables efficient retrieval and alignment of structures with similar 3D shapes.     

Tetrakis(thiadiazolo)porphyrazines. 3. Acid-base Properties and Stability of Tetrakis-3,4-(1,2,5-thiadiazolo)porphyrazine in Sulfuric Acid Solutions

AM1 calculations gave the proton affinities of different types of donor sites in tetrakis-3,4-(1,2,5-thiadiazolo)porphyrazine, H₂{[SN₂)₄PA}, and protonation of the meso-nitrogen atoms was found to be favored. A spectrometric study showed that the basicity of the meso-nitrogen atoms of the porphyrazine macrocycle is strongly diminished and these atoms in CF₃CO₂H are involved in an incomplete acid-base interaction (ABI) to give acid solvates, while a complete ABI (protonation) is found only in the presence of sulfuric acid. The basicity constants of the meso-nitrogen atoms were determined spectrophotometrically in CF₃CO₂H-H₂SO₄. The kinetics of decomposition of the macrocyclic chromophore in concentrated sulfuric acid was studied and a possible mechanism for this process was proposed.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 278–287, February, 2005.     

High-resolution Mn EXAFS of the oxygen-evolving complex in photosystem II: structural implications for the Mn4Ca cluster

The biological generation of oxygen by the oxygen-evolving complex in photosystem II (PS II) is one of nature's most important reactions. The recent X-ray crystal structures, while limited by resolutions of 3.2-3.5 A, have located the electron density associated with the Mn4Ca cluster within the multiprotein PS II complex. Detailed structures critically depend on input from spectroscopic techniques, such as EXAFS and EPR/ENDOR, as the XRD resolution does not allow for accurate determination of the position of Mn/Ca or the bridging and terminal ligand atoms. The number and distances of Mn-Mn/Ca/ligand interactions determined from EXAFS provide important constraints for the structure of the Mn4Ca cluster. Here, we present data from a high-resolution EXAFS method using a novel multicrystal monochromator that show three short Mn-Mn distances between 2.7 and 2.8 A and, hence, the presence of three di-mu-oxo-bridged units in the Mn4Ca cluster. This result imposes clear limitations on the proposed structures based on spectroscopic and diffraction data and provides input for refining such structures.     

Detection of norbolethone,an anabolic steroid never marketed,in athletes' urine

Norbolethone (13-ethyl-17-hydroxy-18,19-dinor-17alpha-pregn-4-en-3-one) is a 19-nor anabolic steroid first synthesized in 1966. During the 1960s it was administered to humans in efficacy studies concerned with short stature and underweight conditions. It has never been reported by doping control laboratories. Norbolethone was identified in two urine samples from one athlete by matching the mass spectra and chromatographic retention times with those of a reference standard. The samples also contained at least one likely metabolite. The samples were also unusual because the concentrations of endogenous steroids were exceptionally low. Since norbolethone is not known to be marketed by any pharmaceutical company, a clandestine source of norbolethone may exist.