Electrical manipulation of oligonucleotides grafted to charged surfaces

The electrical manipulation of short DNA molecules on surfaces offers novel functionalities with fascinating possibilities in the field of bio-interfaces. Here we present systematic investigations of the electrical interactions which govern the structure of oligonucleotides on charged gold surfaces. Successively, we address influences of the applied field strength, the role of DC electrode potentials, in particular for polycrystalline surfaces, as well as screening effects of the surrounding electrolyte solution. Data obtained for single and double stranded DNA exhibit differences which can be attributed to the dissimilar flexibility of the different molecular conformations. A comparison of the experimental results with a basic model shows how the alignment of the molecules adjusts according to a balance between electrically induced ordering and stochastic thermal motions. The presented conclusions are expected to be of general relevance for the behaviour of polyelectrolytes exposed to localized electric fields at interfaces.     

Localized electropolymerization on oxidized boron-doped diamond electrodes modified with pyrrolyl units

This paper describes the functionalization of oxidized boron-doped diamond (BDD) electrodes with N-(3-trimethoxysilylpropyl)pyrrole (TMPP) and the influence of this layer on the electrochemical transfer kinetics as well as on the possibility of forming strongly adhesive polypyrrole films on the BDD interface through electropolymerization. Furthermore, localized polymer formation was achieved on the TMPP-modified BDD interface using the direct mode of a scanning electrochemical microscope (SECM) as well as an electrochemical scanning near-field optical microscope (E-SNOM). Depending on the method used polypyrrole dots with diameters in the range of 1-250 microm are electrogenerated.     

Biocatalytic deuterium- and hydrogen-transfer using over-expressed ADH-'A': enhanced stereoselectivity and 2H-labeled chiral alcohols

Employing the over-expressed highly organic solvent tolerant alcohol dehydrogenase ADH-'A' from Rhodococcus ruber DSM 44541, versatile building blocks, which were not accessible by the wild type catalyst, were obtained in > 99% e.e.; furthermore, employing d8-2-propanol as deuterium source, stereoselective biocatalytic deuterium transfer was made feasible to furnish enantiopure deuterium labeled sec-alcohols on a preparative scale employing a single enzyme.     

Probing the substrate specificity of the catalytically self-sufficient cytochrome P450 RhF from a Rhodococcus sp

Analysis of the substrate specificity of the self-sufficient cytochrome P450 RhF revealed that the enzyme tends to catalyse the dealkylation of substituted alkyl-aryl ethers with shorter alkyl moieties more readily than equivalent compounds with longer alkyl groups.     

A Pulsed EPR and DFT Investigation of the Stabilization of Coordinated Phenoxyl Radicals in a Series of Cobalt Schiff-Base Complexes

We recently demonstrated how the aerobic addition of acetic acid to N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co^II, [Co(1)], leads to the formation of an unusual coordinated Co^III-phenoxyl radical. In this work, some of the structural aspects associated with the Schiff-base-derived ligand (1) that are crucial for the acid-mediated formation of the phenoxyl radical are investigated. For comparison with [Co(1)], we therefore studied the influence of acetic acid on two complexes: (1) the N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-ethane-diamino Co^II complex, [Co(2)], that lacks the cyclohexyl group of [Co(1)], and (2) the N′-disalicylidene-ethylenediamine Co^II salen complex, [Co(3)], that lacks both the tertiary butyl groups and the cyclohexyl groups. It is shown that the cyclohexyl group of [Co(1)] is not involved in the formation or stabilization of the phenoxyl radical, whereas the tertiary butyl groups of [Co(1)] play a crucial role. In addition, the characteristics of the phenoxyl radical, formed after aerobic addition of acetic acid to [Co(2)], are analyzed in detail by pulsed electron paramagnetic resonance, in combination with isotopic labeling. The experimental data are compared to density functional theory computations and to previous data on the acid-mediated phenoxyl radical of [Co(1)].     

A Class of Gorenstein Artin Algebras of Embedding Dimension Four

In this article, we study height four graded Gorenstein ideals I in k[x, y, z, w] such that I ₂ is of height one and generated by three quadrics. After a suitable linear change of variables, I ∩ k[x, y, z] is either Gorenstein or of type two. The former case was studied by Iarrobino and Srinivasan [8 Iarrobino , A. , Srinivasan , H. ( 2005 ). Artininan Gorenstein algebras of embedding dimension four: components of ? Gor (H) for H = (1, 4, 7,…, 1) . Journal of Pure and Applied Algebra 201 : 62 – 96 .[Crossref], [Web of Science ®] , [Google Scholar]] where they give the structure of the ideal and its resolution. We study the latter case and give the structure of these ideals and their minimal resolution. We also explicitly write the form of the generators of I and the maps in the free resolution of R/I.     

The algorithmic beauty of plant roots – an L-System model for dynamic root growth simulation

Understanding the impact of root architecture on plant resource efficiency is important, in particular, in the light of upcoming shortages of mineral fertilizers and changed environmental conditions. In the 1950s, a great number of root systems of European cultivated plants were excavated and studied by L. Kutschera (1960). Her work gave enormous insight into the variety of root system architectures and helped to realize the importance of belowground processes to plant productivity. We analysed the resulting hand drawings by using mathematical modelling and found root system parameters for a newly developed parametric L-System model. In this way we were able to first reproduce the illustrations, second computationally analyse root system traits and finally access the dynamic root architecture development.     

Efficient linear solvers for incompressible flow simulations using Scott‐Vogelius finite elements

Recent research has shown that in some practically relevant situations like multiphysics flows (Galvin et al., Comput Methods Appl Mech Eng, to appear) divergence‐free mixed finite elements may have a significantly smaller discretization error than standard nondivergence‐free mixed finite elements. To judge the overall performance of divergence‐free mixed finite elements, we investigate linear solvers for the saddle point linear systems arising in ((P_k)^d,P _k‐1^disc) Scott‐Vogelius finite element implementations of the incompressible Navier–Stokes equations. We investigate both direct and iterative solver methods. Due to discontinuous pressure elements in the case of Scott‐Vogelius (SV) elements, considerably more solver strategies seem to deliver promising results than in the case of standard mixed finite elements such as Taylor‐Hood elements. For direct methods, we extend recent preliminary work using sparse banded solvers on the penalty method formulation to finer meshes and discuss extensions. For iterative methods, we test augmented Lagrangian and \begin{align*}\mathcal{H}\end{align*} ‐LU preconditioners with GMRES, on both full and statically condensed systems. Several numerical experiments are provided that show these classes of solvers are well suited for use with SV elements and could deliver an interesting overall performance in several applications.© 2012 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2013     

Structural Investigation of New Lithium Amidinates and Guanidinates

A series of potentially useful lithium amidinates and guanidinates were prepared and fully characterized. Treatment of N,N′‐diisopropylcarbodiimide with phenyllithium in diethyl ether afforded the lithium amidinate [PhC(NiPr)₂Li(OEt₂)]₂ ( 1 ). Similar treatment of N,N′‐diorganocarbodiimides R′–N=C=N–R′ [R′ = iPr, cyclohexyl (Cy)] with secondary lithium amides LiNR₂ [R₂ = Et₂, iPr₂, (CH₂)₄] followed by crystallization from THF or 1,4‐dioxane gave the lithium guanidinates [R₂NC(NR′)₂Li(S)]₂ [ 2 : R = Et, R′ = iPr, S = THF; 3 : R₂ = (CH₂)₄, R′ = iPr, S = THF; 4 : R = R′ = iPr, S = ½ 1,4‐dioxane; 5 : R₂ = (CH₂)₄, R′ = Cy, S = 1,4‐dioxane] as crystalline solids. Reaction of N‐lithioaziridine with the corresponding carbodiimides afforded solvent‐deficient [{C₂H₄NC(NiPr₂)₂}₂Li₂(THF)]₂ ( 6 ), and [C₂H₄NC(NEt)(NtBu)Li(THF)]₂ ( 7 ). Crystal structure determination revealed the presence of common ladder‐type dimeric structures for 1 – 5 . Compound 6 exists as a dimer of two ladder‐type dimers in the crystal, and 7 exhibits an unusual dimeric structure comprising an eight‐membered C₂N₄Li₂ ring.     

New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]–

New homoleptic complexes of selected rare‐earth elements containing the unsymmetrically substituted amidinate ligand [MeC(NEt)(NtBu)]^– [= (L)^–] were synthesized and fully characterized. Treatment of in situ‐prepared Li(L) ( 1 ) with anhydrous lanthanide(III) chlorides, LnCl₃ (Ln = Sc, La, Ce, Ho), afforded three different types of amidinate complexes depending on the ionic radius of the central metal atom. The large La³⁺ formed the octa‐coordinate DME solvate La(L)₃(DME) ( 2 ). Using Ce³⁺, the octa‐coordinate “ate” complex Li(THF)[Ce(L)₄] ( 3 ) was formed. Depending on the crystallization conditions, compound 3 could be crystallized in two modifications differing in the coordination environment around Li. In the case of the smaller Sc³⁺ and Ho³⁺ ions, six‐coordinate homoleptic Sc(L)₃ ( 4 ) and Ho(L)₃ ( 5 ) were isolated. The title compounds were fully characterized by spectroscopic and analytical methods as well as single‐crystal X‐ray diffraction. With Ln = La and Ce, several by‐products incorporating lithium, chlorine and/or oxygen were also isolated and structurally characterized.