The use of bis(diphenylphosphino)amines with N-aryl functionalities in selective ethylene tri- and tetramerisation

A systematic study was conducted on the Cr catalysed tri- and tetramerisation of ethylene using bis(diphenylphosphino)amine ligands with N-aryl functionality. This study revealed that the oligomerisation reaction product selectivity is primarily dependent on the structure and size of the N-aryl groups.

Addition of sufficient steric bulk to the N-phenyl group via ortho-alkyl substitution increased the combined 1-hexene and 1-octene selectivity (overall alpha selectivity) to above 82% at an overall 1-octene selectivity of 56%. The introduction of a single carbon spacer between the N-atom and the aryl-moiety, as well as the addition of branching on this carbon, resulted in further selectivity improvements, achieving an overall 1-octene selectivity of 64% and an overall alpha selectivity of 84%. This was obtained at catalyst productivities in excess of 1,000,000 g/g Cr/h.     

Oxidative Reactions of the MoIV Dialkyl Complex [{(3‐CF3C6H4NCH2CH2)2NMe}Mo(CH2SiMe3)2]

The structure of [(CF₃N₂NMe)Mo(CH₂SiMe₃)₂] (in which (CF₃N₂NMe)^2? is [(3‐CF₃C₆H₄NCH₂CH₂)₂NMe]^2?) is approximately trigonal bipyramidal with one axial and one equatorial alkyl ligand. Heating of solutions of [(CF₃N₂NMe)Mo(CH₂SiMe₃)₂] in [D₆]benzene in the presence of five equivalents of 2‐butyne led to diamagnetic [(CF₃N₂NMe)Mo(CHSiMe₃)(η²‐MeC?CMe)], whose structure is approximately square pyramidal with the alkyne occupying the axial site. Addition of one equivalent of cyclohexene sulfide to [(CF₃N₂NMe)Mo(CH₂SiMe₃)₂] at room temperature produced the diamagnetic, dimeric molybdenum(IV) sulfido complex, [{(CF₃N₂NMe)MoS}₂]. This complex is composed of two approximately trigonal bipyramidal centers, each containing one axial and one equatorial sulfur atom. Oxidation of [(CF₃N₂NMe)Mo(CH₂SiMe₃)₂] with hexachloroethane resulted in formation of tetramethylsilane, HCl, and the sparingly soluble, red alkylidyne complex, [{(CF₃N₂NMe)Mo(CSiMe₃)Cl}₂]. This complex forms a dimer through bridging chlorides. The oxidation reactions of [(CF₃N₂NMe)Mo(CH₂SiMe₃)₂] with 2‐butyne, cyclohexene sulfide, or C₂Cl₆ are all proposed to proceed by α‐hydrogen abstraction in the Mo^VI species to yield (initially) the Mo?CHSiMe₃ species and tetramethylsilane.     

Glycosylation site analysis of human alpha-1-acid glycoprotein (AGP) by capillary liquid chromatography-electrospray mass spectrometry

A new anionic surfactant (RapiGest SF) was successfully used for site-specific analysis of glycosylation in human alpha-1-acid glycoprotein (AGP). By means of this analytical approach combined with capillary HPLC-mass spectrometry (and tandem mass spectrometry), the N-linked glycosylation pattern of AGP was explored. On the basis of mass matching and MS/MS experiments ca 80 different AGP-derived glycopeptides were identified. Glycosylation shows a markedly different pattern for the various glycosylation sites. At sites I and II, triantennary complex-type oligosaccharides predominate and at sites III, IV and V, tetra-antennary complex-type oligosaccharides predominate. Sites IV and V show the presence of additional N-acetyl lactosamine (Gal-GlcNAc) units (even higher degree of branching and/or longer antennae are also present).     

Marine Sediments and Snow from Ross Sea Region (Antarctica) Dating by 210Pb Method

Abstract

²¹⁰Pb is widely used to determine accumulation rates in order to obtain a time scale in environmental samples. The most accurate method uses the determination of ²¹⁰Pb via its grand-daughter ²¹⁰Po by alpha spectrometry. Unfortunately this method requires a complex wet-chemistry procedure to achieve the separation of ²¹⁰Po from its matrix. In this work a simplified procedure for the chemical separation of ²¹⁰Po is proposed and applied to three marine sediment cores and a 10 m snow core collected in Antarctica. The calculated sedimentation rates for marine sediments range from 0.053 to 0.071 cm y^?1. The mean annual accumulation rate for the snow is 16.6 cm y^?1 w.e. A comparison with literature data in the same region is given.     

Two new guaianolide-type sesquiterpenoids from Kadsura interior

Two new guaianolide-type sesquiterpenoids,4β,9β-dihydroxy-1α,5α-H-guaia-6,10(14)-dien(1) and 4β,9β,10α-trihydroxy-1α,5α-H-guaia-6-en(2),along with four known sesquiterpenoids(3a,3b,4 and 5),were isolated from Kadsura interior.Their structures and configurations were elucidated by spectroscopic methods including 2D-NMR and HR-MS techniques.Compounds 3a and 3b were obtained as a pair of enantiomers,and their structure and absolute configuration were established from their extensive NMR spectra and by single-crystal X-ray analysis.     

Differential geometric analysis of alterations in MH α‐helices

Antigen presenting cells present processed peptides via their major histocompatibility (MH) complex to the T cell receptors (TRs) of T cells. If a peptide is immunogenic, a signaling cascade can be triggered within the T cell. However, the binding of different peptides and/or different TRs to MH is also known to influence the spatial arrangement of the MH α‐helices which could itself be an additional level of T cell regulation. In this study, we introduce a new methodology based on differential geometric parameters to describe MH deformations in a detailed and comparable way. For this purpose, we represent MH α‐helices by curves. On the basis of these curves, we calculate in a first step the curvature and torsion to describe each α‐helix independently. In a second step, we calculate the distribution parameter and the conical curvature of the ruled surface to describe the relative orientation of the two α‐helices. On the basis of four different test sets, we show how these differential geometric parameters can be used to describe changes in the spatial arrangement of the MH α‐helices for different biological challenges. In the first test set, we illustrate on the basis of all available crystal structures for (TR)/pMH complexes how the binding of TRs influences the MH helices. In the second test set, we show a cross evaluation of different MH alleles with the same peptide and the same MH allele with different peptides. In the third test set, we present the spatial effects of different TRs on the same peptide/MH complex. In the fourth test set, we illustrate how a severe conformational change in an α‐helix can be described quantitatively. Taken together, we provide a novel structural methodology to numerically describe subtle and severe alterations in MH α‐helices for a broad range of applications. © 2013 Wiley Periodicals, Inc.     

Heterocyclic Substitutions Greatly Improve Affinity and Stability of Folic Acid towards FRα. an In Silico Insight

Folate receptor alpha (FRα) is known as a biological marker for many cancers due to its overexpression in cancerous epithelial tissue. The folic acid (FA) binding affinity to the FRα active site provides a basis for designing more specific targets for FRα. Heterocyclic rings have been shown to interact with many receptors and are important to the metabolism and biological processes within the body. Nineteen FA analogs with substitution with various heterocyclic rings were designed to have higher affinity toward FRα. Molecular docking was used to study the binding affinity of designed analogs compared to FA, methotrexate (MTX), and pemetrexed (PTX). Out of 19 FA analogs, analogs with a tetrazole ring (FOL03) and benzothiophene ring (FOL08) showed the most negative binding energy and were able to interact with ASP81 and SER174 through hydrogen bonds and hydrophobic interactions with amino acids of the active site. Hence, 100 ns molecular dynamics (MD) simulations were carried out for FOL03, FOL08 compared to FA, MTX, and PTX. The root mean square deviation (RMSD) and root mean square fluctuation (RMSF) of FOL03 and FOL08 showed an apparent convergence similar to that of FA, and both of them entered the binding pocket (active site) from the pteridine part, while the glutamic part was stuck at the FRα pocket entrance during the MD simulations. Molecular mechanics Poisson-Boltzmann surface accessible (MM-PBSA) and H-bond analysis revealed that FOL03 and FOL08 created more negative free binding and electrostatic energy compared to FA and PTX, and both formed stronger H-bond interactions with ASP81 than FA with excellent H-bond profiles that led them to become bound tightly in the pocket. In addition, pocket volume calculations showed that the volumes of active site for FOL03 and FOL08 inside the FRα pocket were smaller than the FA–FRα system, indicating strong interactions between the protein active site residues with these new FA analogs compared to FA during the MD simulations.     

Doping Polysulfone Membrane with Alpha‐Tocopherol and Alpha‐Lipoic Acid for Suppressing Oxidative Stress Induced by Hemodialysis Treatment

The reduction of free radicals by bioactive membranes used for hemodialysis treatment is an important topic due to the constant rise of oxidative stress‐associated cardiovascular mortality by hemodialysis patients. Therefore, it is urgent to find an effective solution that helps to solve this problem. Polysulfone membranes enriched with α‐lipoic acid, α‐tocopherol, and with both components are fabricated by spin coating. The antioxidant properties of these membranes are evaluated in vitro by determining the lipid‐peroxidation level and the total antioxidant status of the blood plasma. The biocompatibility is assessed by quantifying the protein adsorption, platelet adhesion, complement activation, and hemolytic effect. All types of membranes show in vitro antioxidant activity and a trend to reduce oxidative stress in vivo; the best results show membranes prepared with a combination of both compounds and prove to be nonhemolytic and hemocompatible. Moreover, the membrane specific separation ability for the main waste products is not affected by antioxidants incorporation.     

Higher-Order (F,α,β,ρ,d,E)-Convexity in Fractional Programming

In this paper we define higher order (F,α,β,ρ,d,E)-convex function with respect to E-differentiable function K and obtain optimality conditions for nonlinear programming problem (NP) from the concept of higher order (F,α,β,ρ,d)-convexity. Here, we establish Mond-Weir and Wolfe duality for (NP) and utilize these duality in nonlinear fractional programming problem.