Ion‐Pair Complexation with a Cavitand Receptor

The capability of resorcinarenes to bind anions within the alkyl feet at the lower rim has been exploited as the starting point for developing a new cavitand able to engulf contact ion pairs of primary ammonium salts in chlorinated solvents with association constants (K_ass) in the range of 10³–10⁴ M ^?1. Methylene bridges were introduced into the upper rim to freeze the resorcinarene in the cone conformation with the four H_down protons converging in the lower pocket, thereby maximizing the CH–anion interactions responsible for the anion binding. Four additional phosphate moieties were introduced into the lower rim in close proximity to the anionic site to provide hydrogen‐bonding‐acceptor P?O groups and promote cation complexation at the bottom of the cavitand. The binding ability of the synthesized ligands was analyzed by ¹H NMR spectroscopy and, when possible, by isothermal titration calorimetry (ITC); the data were in agreement when complementary techniques were used.     

Interplay of Magnetic Exchange Interactions and Ni?S?Ni Bond Angles in Polynuclear Nickel(II) Complexes

The ability of bridging thiophenolate groups (RS^?) to transmit magnetic exchange interactions between paramagnetic Ni^II ions is examined. Specific attention is paid to complexes with large Ni? SR? Ni angles. For this purpose, dinuclear [Ni₂L¹(μ‐OAc)?I₂][I₅] ( 2 ) and trinuclear [Ni₃L²(OAc)₂][BPh₄]₂ ( 3 ), where H₂L¹ and H₂L² represent 24‐membered macrocyclic amino‐thiophenol ligands, are prepared and fully characterized by IR‐ and UV/Vis spectroscopy, X‐ray crystallography, static magnetization M measurements and high‐field electron spin resonance (HF‐ESR). The dinuclear complex 2 has a central N₃Ni₂(μ‐S)₂(μ‐OAc)Ni₂N₃ core with a mean Ni? S? Ni angle of 92°. The macrocycle L² supports a trinuclear complex 3 , with distorted octahedral N₂O₂S₂ and N₂O₃S coordination environments for one central and two terminal Ni^II ions, respectively. The Ni? S? Ni angles are at 132.8° and 133.5°. We find that the variation of the bond angles has a very strong impact on the magnetic properties of the Ni complexes. In the case of the Ni₂‐complex, temperature T and magnetic field B dependencies of M reveal a ferromagnetic coupling J=?29 cm^?1 between two Ni^II ions (H=JS₁S₂). HF‐ESR measurements yield a negative axial magnetic anisotropy (D<0) which implies a bistable (easy axis) magnetic ground state. In contrast, for the Ni₃‐complex we find an appreciable antiferromagnetic coupling J′=97 cm^?1 between the Ni^II ions and a positive axial magnetic anisotropy (D>0) which implies an easy plane situation.     

Retention of functional polymers in liquid adsorption chromatography: Effect of the end groups in PEGs and their methyl ethers in different mobile phases

It is shown that the end group parameter, which describes the influence of the end group on retention, can be determined in RP chromatography from two chromatograms of a nonfunctional and a monofunctional sample, if a sufficient number of peaks with the same number of repeat units in each sample can be reasonably resolved and identified. The same procedure can also be applied for pairs of di‐ and monofunctional polymers. End group parameters have been determined in three different mobile phases: acetonitrile–water, acetone–water and methanol–water of different compositions. The temperature dependence of the interaction parameter of the repeat unit and the end group parameter has been found to be different, which allows a fine‐tuning of retention.     

On the combined use of discrete solvent models and continuum descriptions of solvent effects in ligand exchange reactions: a case study of the uranyl(VI) aquo ion

Modeling of the solvent is important when using quantum chemical methods for the assignment of mechanisms from experimental studies of the exchange of water between metal aquo ions and the bulk solvent. In the present study, we have investigated if and how the mechanisms for water exchange in the UO₂(OH₂) ₅ ²⁺ –H₂O system is affected by the choice of chemical models for the second coordination sphere and physical models for describing the cavity in conductor-like polarizable continuum (CPCM) models. In the first case, we have compared models with one and five waters in the second coordination sphere. For both models, we have compared cavities in which each atom is assigned one spherical cavity and one in which the water molecules are described by a single spherical cavity (the United Atom model). There are significant differences in the relative energy of dissociative and associative intermediates; however, they are not large enough to affect the conclusion that the water exchange proceeds through an associative/interchange mechanism.     

SERS Labels for Red Laser Excitation: Silica‐Encapsulated SAMs on Tunable Gold/Silver Nanoshells

In a glass house : Silica‐encapsulated self‐assembled monolayers (SAMs) on tunable gold/silver nanoshells were used as labels for surface‐enhanced Raman scattering (SERS). This concept combines the spectroscopic advantages arising from maximum surface coverage and uniform molecular orientation of the Raman reporter molecules within the complete monolayer together with the high chemical and mechanical stability of the glass shell.

     

On the Stability Analysis of Decoupled Solution Schemes

Many problems in engineering, physics or other disciplines require an integrated treatment of coupled fields. These problems are characterised by a dynamic interaction among two or more physically or computationally distinct components, where the undergoing mathematical model commonly consists of a system of coupled PDE. Considerable progress has been made in the development of appropriate computational schemes to solve such coupled PDE systems. These attempts have resulted in various monolithic and decoupled numerical solution approaches. Despite the unconditional stability offered by implicit monolithic solution strategies, their use is not always recommended. The reason mainly lies in the complexity of the resulting system of equations and the limited flexibility in choosing appropriate time integrators for individual components. This has motivated the elaboration of tailored decoupled solution schemes, which follow the idea of splitting the problem into several sub-problems. But selection of the way of splitting can have a direct influence on the stability of the resulting solution algorithm. This necessitates the stability analysis of such an algorithm. Here, we introduce a general framework for the stability analysis of decoupled solution schemes. The approach is then used to study the stability behaviour of established decoupling strategies applied to typical volume- and surface-coupled problems, namely, coupled problems of thermoelasticity, porous media dynamics and structure-structure interaction. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

DIESEL-MP2: a new program to perform large-scale multireference-MP2 computations

This article presents a new MR‐MP2 code (Multi‐Reference Møller–Plesset 2nd order) suitable for the computation MR‐MP2 energies of extended systems with strong near degeneracy effects (e.g., open shell systems). It is based on the DIESEL program package developed by Hanrath and Engels. Due to improved algorithms the new code is able to handle systems with 400–500 basis functions and more than 100 electrons. The code is made for parallel computers with distributed memory, but can also be run on local machines. It possesses two integral interfaces (MOLCAS, TURBOMOLE). The algorithms are briefly introduced and timings for the Neocarzinostatin chromophore are presented. The efficiencies of the codes obtained with Intel or GNU compilers are compared. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1055–1062, 2006     

A 15N-aided artificial atmosphere gas flow technique for online determination of soil N2 release using the zeolite Köstrolith SX6

N2 is one of the major gaseous nitrogen compounds released by soils due to N-transformation processes. Since it is also the major constituent of the earth's atmosphere (78.08% vol.), the determination of soil N2 release is still one of the main methodological challenges with respect to a complete evaluation of the gaseous N-loss of soils. Commonly used approaches are based either on a C2H2 inhibition technique, an artificial atmosphere or a 15N-tracer technique, and are designed either as closed systems (non-steady state) or gas flow systems (steady state). The intention of this work has been to upgrade the current gas flow technique using an artificial atmosphere for a 15N-aided determination of the soil N2 release simultaneously with N2O. A 15N-aided artificial atmosphere gas flow approach has been developed, which allows a simultaneous online determination of N2 as well as N2O fluxes from an open soil system (steady state). Fluxes of both gases can be determined continuously over long incubation periods and with high sampling frequency. The N2 selective molecular sieve K?strolith SX6 was tested successfully for the first time for dinitrogen collection. The presented paper mainly focuses on N2 flux determination. For validation purposes soil aggregates of a Haplic Phaeozem were incubated under aerobic (21 and 6 vol.% O2) and anaerobic conditions. Significant amounts of N2 were released only during anaerobic incubation (0.4 and 640.2 pmol N2 h(-1) g(-1) dry soil). However, some N2 formation also occurred during aerobic incubation. It was also found that, during ongoing denitrification, introduced [NO3]- will be more strongly delivered to microorganisms than the original soil [NO3]-.     

Ion mobility spectrometric investigation of aromatic cations in the gas phase

In this work, ion mobility (IM) spectra of more than 50 aromatic compounds were recorded with a laser-based IM spectrometer at atmospheric pressure. IM spectra of PAH in the laser desorption experiment show a high complexity resulting from the occurrence of monomeric, dimeric, and oligomeric cluster ions. The mobilities of all compounds were determined in helium as drift gas. This allows the calculation of the diffusion cross sections (Omega(calc)) on the basis of the exact hard sphere scattering model and their comparison with the experimentally determined diffusion cross sections (Omega(exp)). Extended Omega(exp)/Omega(calc) and Omega(exp)/mass correlations were performed in order to gain insight into conformational properties of cationic alkyl benzenes and internal rotation of phenyl rings in aromatic ions. This is demonstrated with some examples, such as the evaluation of the dihedral angle of the ions of 9,10-diphenylanthracene, o- and m-terphenyl, and 1,2,3- and 1,3,5-triphenylbenzene. Furthermore, sandwich and T-structures of dimeric PAH cations are discussed. The analysis was extended to oligomeric ions with up to nine monomer units. Experimental evidence is presented suggesting the formation of pi-stacks with a transition toward modified pi-stacks with increasing cluster size. The distance between monomeric units in dimeric and oligomeric ions was obtained.