Investigating inclusion complexes using quantum chemical methods

Quantum chemistry has firmly established itself as a reliable method for investigating present-day problems in biological and materials chemistry. Understanding inclusion complexes represents one of the cutting edges of simulation sciences. In this tutorial review, we focus on the role and composition of non-covalent interactions, which are essential when studying inclusion complexes. A selected set of recently developed pragmatic methods used to study inclusion complexes are then surveyed including e.g. dispersion corrected DFT, double-hybrid functionals and spin-component scaled MP2. Finally, three case studies are outlined: (a) endohedral fullerene complexes, (b) buckyball catcher and (c) resorcinarene capsule. These case studies were carefully chosen to help illustrate how one may accurately investigate inclusion complexes, at a modest computational cost, using state-of-the-art quantum chemical methods (67 references).     

Elastic Properties of Muscle Tissue: Comparison of an Inverse Finite Element Approach and Homogeneous Deformation

Parameters of material models are commonly identified by fitting predicted stress-stretch relations to experimentally derived ones, assuming homogeneous deformation. This approach has been compared with an inverse finite element strategy, where an FE model of the actual measurement set-up is created to obtain stress-stretch data. Compressive tests of skeletal muscle tissue have been conducted for different fiber orientations, with a stereo camera system capturing the geometry of the sample. The material exhibited an exponential increase in stiffness with increasing stretch, with large differences related to the fiber orientation; this behavior is described well by a model for arterial layers. Assuming homogeneous deformation led to significantly different stress-stretch curves indicating that this assumption is unrealistic in this case. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Solid‐phase cadmium speciation in soil using L3‐edge XANES spectroscopy with partial least‐squares regression

Cadmium (Cd) has a high toxicity and resolving its speciation in soil is challenging but essential for estimating the environmental risk. In this study partial least‐square (PLS) regression was tested for its capability to deconvolute Cd L₃‐edge X‐ray absorption near‐edge structure (XANES) spectra of multi‐compound mixtures. For this, a library of Cd reference compound spectra and a spectrum of a soil sample were acquired. A good coefficient of determination (R²) of Cd compounds in mixtures was obtained for the PLS model using binary and ternary mixtures of various Cd reference compounds proving the validity of this approach. In order to describe complex systems like soil, multi‐compound mixtures of a variety of Cd compounds must be included in the PLS model. The obtained PLS regression model was then applied to a highly Cd‐contaminated soil revealing Cd₃(PO₄)₂ (36.1%), Cd(NO₃)₂·4H₂O (24.5%), Cd(OH)₂ (21.7%), CdCO₃ (17.1%) and CdCl₂ (0.4%). These preliminary results proved that PLS regression is a promising approach for a direct determination of Cd speciation in the solid phase of a soil sample.     

Synthesis of spirohydantoins and spiro-2,5-diketopiperazines via resin-bound cyclic alpha,alpha-disubstituted alpha-amino esters

A seven-step solid-phase synthesis of spirohydantoins and an eight-step solid-phase synthesis of spiro-2,5-diketopiperazines is reported. Key intermediate in the synthesis of both compound libraries is the resin-bound cyclic alpha,alpha-disubstituted alpha-amino ester, which can be obtained after selective homogeneous reduction of the aliphatic nitro ester using tin(II) chloride dihydrate. Nitro ester, in turn, is synthesized by a high-pressure-assisted [4 + 2] cycloaddition of resin-bound nitro alkene and butadiene, whereas nitro alkene is obtained by a Knoevenagel condensation of resin-bound nitro acetate with an imine. Novel spirohydantoins are obtained by isocyanate coupling with the resin-bound amino ester 5, followed by cyclization cleavage using a base. Novel spiro-2,5-diketopiperazines are obtained by PyBOP coupling of a Fmoc-protected amino acid with resin-bound amino ester, followed by Fmoc deprotection and an acid-assisted cyclization cleavage. After preparation of seven different resin-bound alpha,alpha-disubstituted alpha-amino esters, a 7 x 8 compound library of spirohydantoins was synthesized using eight different isocyanates, and a 7 x 8 compound library of spiro-2,5-diketopiperazines was synthesized using eight different Fmoc amino acids.     

Efficient library synthesis of imidazoles using a multicomponent reaction and microwave irradiation

Optimization of Radziszewski's four-component reaction employing a microwave-assisted protocol, led to a small library of 48 imidazoles with a success rate of 65% (conversion > 45%). All three diversity points of the four-component reaction were varied. Aromatic and aliphatic inputs were successfully implemented and mono-, di-, tri- and tetrasubstituted imidazoles with various substitution patterns were synthesized. Furthermore, unsymmetrical diketones could successfully be used which improved the intrinsic diversity of the method significantly. If the unsymmetrical diketone 1,2-phenylpropanedione (R¹ and R²) was used two regioisomers were formed. Depending on the type of amine (R⁴) and aldehyde (R³) applied, regioselectivity was modest to good. Based on these results, a reaction mechanism is proposed.     

Self-organization in systems of treadmilling filaments

The cytoskeleton is an important substructure of living cells, playing essential roles in cell division, cell locomotion, and the internal organization of subcellular components. Physically, the cytoskeleton is an active polar gel, that is, a system of polar filamentous polymers, which is intrinsically out of thermodynamic equilibrium. Active processes are notably involved in filament growth and can lead to net filament assembly at one end and disassembly at the other, a phenomenon called treadmilling. Here, we develop a framework for describing collective effects in systems of treadmilling filaments in the presence of agents regulating filament assembly. We find that such systems can self-organize into asters and moving filament blobs. We discuss possible implications of our findings for subcellular processes.     

Methode zur Sichtbarmachung der Vulkanisations-Reaktion im Kautschuk

Zusammenfassung Es wurde geschildert, wie man unter Beachtung ganz bestimmter Voraussetzungen hinsichtlich Plastizit?t und Homogenit?t der Versuchsmischung den Verlauf der Vulkanisationsreaktion im Kautschuk auf Grund der Dehnungsdoppelbrechung im Polarisationsi-Mikroskop sichtbar machen kann. Die Reaktion geht offenbar in der Form vor sich, da? sich zun?chst von Reaktionskeimen ausgehend, feine Adern von vulkanisiertem Kautschuk bilden, welche sich bei fortschreitender Reaktion zu einem immer enger werdenden System verdichten.     

The Role of Teachers' Beliefs and Knowledge in the Adoption of a Reform‐Based Curriculum

Science as inquiry is a key content standard in the National Science Education Standards; however, few secondary science teachers successfully and consistently implement inquiry‐based instruction in their classrooms. This research examines the role of reform‐based curricular materials in influencing the classroom practices of 12 high school chemistry teachers and investigates the role of the teachers' knowledge and beliefs in their implementation of the reform‐based chemistry curriculum. Qualitative and quantitative data were collected in the form of beliefs interviews and classroom observations. The teachers' classroom practices were measured prior to and during the field test of the reform‐based chemistry curriculum. Analysis of the data revealed that teachers' classroom practice became more reform‐based in the presence of the new curriculum; however, the degree of change is related to the teachers' beliefs about teaching and learning, depth of chemistry knowledge, and years of teaching experience. Experienced, out‐of‐discipline teachers with transitional or student‐centered teaching beliefs demonstrated the most growth in reform‐based teaching practices. This study reinforces the need for reform‐based curriculum to assist teachers in implementing the intent of the National Science Education Standards.     

Determination of Aroclor 1260 in soil samples by gas chromatography with mass spectrometry and solid‐phase microextraction

A novel fast screening method was developed for the determination of polychlorinated biphenyls that are constituents of the commercial mixture, Aroclor 1260, in soil matrices by gas chromatography with mass spectrometry combined with solid‐phase microextraction. Nonequilibrium headspace solid‐phase microextraction with a 100 μm polydimethylsiloxane fiber was used to extract polychlorinated biphenyls from 0.5 g of soil matrix. The use of 2 mL of saturated potassium dichromate in 6 M sulfuric acid solution improved the reproducibility of the extractions and the mass transfer of the polychlorinated biphenyls from the soil matrix to the microextraction fiber via the headspace. The extraction time was 30 min at 100°C. The percent recoveries, which were evaluated using an Aroclor 1260 standard and liquid injection, were within the range of 54.9–65.7%. Two‐way extracted ion chromatogram data were used to construct calibration curves. The relative error was <±15% and the relative standard deviation was <15%, which are respective measures of the accuracy and precision. The method was validated with certified soil samples and the predicted concentrations for Aroclor 1260 agreed with the certified values. The method was demonstrated to be linear from 10 to 1000 ng/g for Aroclor 1260 in dry soil.     

XPS and ToF‐SIMS characterization of a Finemet surface: effect of heating

X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) were used to study the surface composition and electronic structure of Finemet, Fe₇₃Si_15.8B_7.2Cu₁Nb₃, in the original amorphous state and after gradual heating in vacuum to a temperature of 400 °C and cooling back to room temperature. It was found that relaxation processes occurring during heat treatment well below the crystallization onset caused the physico‐chemical state of Finemet surface to change irreversibly. In the relaxed alloy, the surface originally covered with the native air‐formed oxide was significantly enriched with elemental iron and depleted of other alloy constituents compared with the original state. Yet in the as‐quenched state, clustering of copper atoms on the Finemet surface was detected which was enhanced by heating. The thermal treatment resulted in the selective reduction of iron oxides and caused noticeable changes in the valence band structure and the Fe L₃VV Auger spectrum associated with atomic redistribution. Copyright © 2009 John Wiley & Sons, Ltd.