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.     

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.     

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.     

Adsorption of cationic cellulose derivative/anionic surfactant complexes onto solid surfaces. II. Hydrophobized silica surfaces

The effect of the anionic surfactant SDS (sodium dodecyl sulfate) on the adsorption behavior of cationic hydroxyethyl cellulose (Polymer JR-400) and hydrophobically modified cationic cellulose (Quatrisoft LM-200) at hydrophobized silica has been investigated by null ellipsometry and compared with the previous data for adsorption onto hydrophilic silica surfaces. The adsorbed amount of LM-200 is found to be considerably larger than the adsorbed amount of JR-400 at both surfaces. Both polymers had higher affinity toward hydrophobized silica than to silica. The effect of SDS on polymer adsorption was studied under two different conditions: adsorption of polymer/SDS complexes from premixed solutions and addition of SDS to preadsorbed polymer layers. Association of the surfactant to the polymer seems to control the interfacial behavior, which depends on the surfactant concentration. For the JR-400/SDS complex, the adsorbed amount on hydrophobized silica started to increase progressively from much lower SDS concentrations, while the adsorbed amount on silica increased sharply only slightly below the phase separation region. For the LM-200/SDS complex, the adsorbed amounts increased progressively from very low SDS concentrations at both surfaces, and no large difference in the adsorption behavior was observed between two surfaces below the phase separation region. The complex desorbed from the surface at high SDS concentrations above the critical micelle concentration. The reversibility of the adsorption of polymer/SDS complexes upon rinsing was also investigated. When the premixed polymer/SDS solutions at high SDS concentrations (>5 mM) were diluted by adding water, the adsorbed amount increased due to the precipitation of the complex. The effect of the rinsing process on the adsorbed layer was determined by the hydrophobicity of the polymer and the surface.     

Hydration and dielectric properties of aqueous solutions of protonated diallylmethylammonium polymer: transition from monomer to polymer

Abstract

The high-frequency dielectric relaxation of aqueous solutions of protonated diallylammonium polyelectrolyte, namely poly(diallylmethylammonium trifluoroacetate) has been studied at the maximum water dispersion frequencies, 7.5–25?GHz, and temperatures of 288, 298, and 308?K. Dielectric relaxation parameters have been calculated and compared with similar characteristics of aqueous solutions of monomer, diallylmethylammonium trifluoroacetate, and pyrrolidinium trifluoroacetate salt simulated structure of pyrrolidinium polymer link. It has been concluded that although the monomer features hydrophobic hydration, its polymer exhibits hydrophilic hydration properties. This change is related to conformation of hydrophilic-hydrophobic polycations in aqueous solutions and the change in the structure of polymer links.     

Amidation of deltacyclene and hexacyclic norbornadiene dimers with acetonitrile and water catalyzed by FeCl3·6H2O

Abstract

FeCl₃·6H₂O-catalyzed Ritter amidation of deltacyclene and hexacyclic norbornadiene dimers containing both a double bond and a three-carbon ring in the molecule with acetonitrile and water was performed. Depending on the hydrocarbon structure, the reaction proceeds via C-C bond cleavage in the three-carbon ring or at the double bond to form the corresponding N-acetamides.     

Bifunctional activation of amine-boranes by the W/Pd bimetallic analogs of “frustrated Lewis pairs”

The reaction between basic [(PCP)Pd(H)] (PCP = 2,6-(CH₂P(t-C₄H₉)₂)₂C₆H₄) and acidic [LWH(CO)₃] (L = Cp (1a), Tp (1b); Cp = η⁵-cyclopentadienyl, Tp = κ³-hydridotris(pyrazolyl)borate) leads to the formation of bimolecular complexes [LW(CO)₂(μ-CO)⋯Pd(PCP)] (4a, 4b), which catalyze amine-borane (Me₂NHBH₃, ^tBuNH₂BH₃) dehydrogenation. The combination of variable-temperature (¹H, ³¹P{¹H}, ¹¹B NMR and IR) spectroscopies and computational (ωB97XD/def2-TZVP) studies reveal the formation of an η¹-borane complex [(PCP)Pd(Me₂NHBH₃)]⁺[LW(CO₃)]⁻ (5) in the first step, where a BH bond strongly binds palladium and an amine group is hydrogen-bonded to tungsten. The subsequent intracomplex proton transfer is the rate-determining step, followed by an almost barrierless hydride transfer. Bimetallic species 4 are easily regenerated through hydrogen evolution in the reaction between two hydrides.

Bimetallic complexes [LW(CO)₂(μ-CO)⋯Pd(PCP)] cooperatively activate amine-boranes for their dehydrogenation via N–H proton tunneling at RDS and H₂ evolution from two neutral hydrides.