Bioinspired Nanodevice Based on the Folic Acid/Titanium Dioxide System

A new bioinspired nanomaterial has been obtained by chemisorption of folic acid onto nanocrystalline titanium dioxide. The organic chromophore is linked with the semiconductor surface via the glutamate chain and anchored with the carboxylate group. The geometry and electronic structure of the chromophore was studied in detail with DFT. Photoelectrochemical studies revealed photosensitization of the new material towards visible light. The photoelectrodes composed of the folic acid/titanium dioxide hybrid material generated photocurrent over a 300–600‐nm window. Moreover, the direction of the photocurrent could be changed from anodic to cathodic and vice versa by application of the appropriate photoelectrode potential. Photoelectrochemical and spectroscopic studies allowed the elucidation of the mechanism of photocurrent switching. Photoelectrodes composed of folate‐modified titanium dioxide may serve as a simple model of optoelectronic switches and may constitute the basis for molecular photoelectronic devices.     

Molecular mechanical devices based on quinone-pyrrole and quinone-indole dyads: a computational study

A set of intramolecularly connected dyads consisting of a quinone unit and a pyrrole or indole moiety have been designed and evaluated in quantum-chemical calculations. It is shown computationally for several systems, depending on the length and attachment points of the interconnecting chains, that a reduction of the quinone to the semiquinone radical anion or quinolate dianion state leads to a reversible intramolecular reorientation from a pi-stacked to a T-stacked arrangement. In the rearranged structures, a hydrogen bond from the pyrrole or indole N-H function to the semiquinone or quinolate pi-system is created upon reduction. In some systems, hydrogen bonds to the semiquinone or quinolate oxygen atoms are partly feasible and will be preferred over T-stacking. The choice of systems has been based on recent computational observations related to photosystem I. Systems with pyrrole or indole units should provide a better basis for the envisioned molecular motor than recently proposed quinone-benzene dyads. The intramolecular interactions modify the quinone redox potentials. Electronic g-tensors have been computed for the semiquinone states. These reflect characteristically the presence and nature of hydrogen bonds to the semiquinone and represent suitable electron paramagnetic resonance spectroscopic probes for the preferred structures. Intramolecular proton transfer is possible in the dianionic state.     

FTIR-ATR investigations of an α-helix to β-sheet conformational transition in poly(l-lysine)

A promising application of the multivariate curve resolution based on alternating least squares (MCR-ALS) method is reported for the analysis of the temperature-dependent conformational changes in poly(l-lysine) (PLL). The MCR-ALS approach has enabled detection of three structural components developed during the melting experiment. Most important is an infrared signature of the intermediate component described as a mixture of native α-helical conformation and its extended forms.     

Smectic behaviour of methyl 4-alkoxybenzoates with a partially fluorinated alkyl chain

A series of 4-alkoxybenzoic acids 1[m,n] and their methyl esters 2[m,n] containing a partially fluorinated alkyl chain was prepared and their physical properties were investigated by optical, thermal and powder X-ray diffraction (XRD) methods. The former exhibits an SmC phase, while the latter form an SmA phase. XRD analysis indicated liquid-like character of the linking alkyl chains, and showed a decreasing layer thermal expansion coefficient from positive to negative upon increasing the degree of fluorination. The new esters 2[m,n] expanded the series and permitted analysis of trends in thermal stability of the SmA phase. The results demonstrate that the SmA–I transition temperature increases by about +20 K per CF₂CF₂ unit, and is destabilised by –5.6 K upon extending the hydrocarbon part by each CH₂CH₂ group. Data for the expanded series 2[m,n] were used for comparative analysis of mesogenic behaviour in two other series of derivatives of 1[m,n]. Synthetic methods for 1[m,n] and 2[m,n] are reviewed.     

Asymmetric Dearomative (3+2)-Cycloaddition Involving Nitro-Substituted Benzoheteroarenes under H-Bonding Catalysis

In our studies, the organocatalytic 1,3-dipolar cycloaddition between 2-nitrobenzofurans or 2-nitrobenzothiophene and N-2,2,2-trifluoroethyl-substituted isatin imines has been developed. The reaction has been realized by employing bifunctional organocatalysis, with the use of squaramide derivative being crucial for the stereochemical efficiency of the process. The usefulness of the cycloadducts obtained has been confirmed in selected transformations, including aromative and non-aromative removal of the nitro group.     

Influence of dynamic brake pad properties on automotive disk brake squeal

Comparing different methods of characterizing dynamic properties of brake pad materials clearly shows, that those properties strongly depend on the boundary conditions as well as on amplitude and frequency in the excitation. Actually simulations of brake squeal suffer on the missing of correct material parameters identified under conditions relevant for squeal. The present paper gives inside into a method for the measurement and identification of linear and nonlinear brake pad material parameters identified under correct boundary conditions. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the mechanism of anion desorption from DNA induced by low energy electrons

Our knowledge of the mechanisms of radiation damage to DNA induced by secondary electrons is still very limited, mainly due to the large sizes of the system involved and the complexity of the interactions. To reduce the problem to its simplest form, we investigated specific electron interactions with one of the most simple model system of DNA, an oligonucleotide tetrameter compound of the four bases. We report anion desorption yields from a thin solid film of the oligonucleotide GCAT induced by the impact of 3-15 eV electrons. All observed anions (H-, O-, OH-, CN-, and OCN-) are produced by dissociative electron attachment to the molecule, which results in desorption peaks between 6 and 12 eV. Above 14 eV nonresonant dipolar dissociation dominates the desorption yields. By comparing the shapes and relative intensities of the anion yield functions from GCAT physisorbed on a tantalum substrate with those obtained from isolated DNA basic subunits (i.e., bases, deoxyribose, and phosphate groups) from either the gas phase or condensed phase experiments, it is possible to obtain more details on the mechanisms involved in low energy electron damage to DNA, particularly on those producing single strand breaks.     

Protein-cofactor interactions and EPR parameters for the Q(H) quinone binding site of quinol oxidase. A density functional study

Recent multifrequency EPR studies of the "high-affinity" quinone binding site of quinol oxidase (Q(H) site) have suggested a very asymmetric hydrogen-bonding environment for the semiquinone radical anion state. Single-sided hydrogen bonding to the O1 carbonyl position was one of the proposals, which contrasts with some previous experimental indications. Here density functional calculations of the EPR parameters (g-tensors, 13C, 1H, and 17O hyperfine tensors) for a wide variety of supermolecular model complexes have been used to provide insight into the detailed relations among structure, environment, and EPR parameters of ubisemiquinone radical anions. A single-sided binding model is not able to account for the experimentally observed low g(x) component of the g-tensor or for the observed magnitude of the asymmetry of the 13C carbonyl HFC tensors. Based on the detailed comparison between computation and experiment, a model with two hydrogen bonds to O1 and one hydrogen bond to O4 is suggested for the Q(H) site, but a model with one more hydrogen bond on each side cannot be excluded. Several general conclusions on the interrelations between EPR parameters and hydrogen bond patterns of ubisemiquinones in proteins are provided.