Coverage-dependent adsorption geometry of octithiophene on Au(111)

The adsorption behavior of α-octithiophene (8T) on the Au(111) surface as a function of 8T coverage has been studied with low-temperature scanning tunneling microscopy, high resolution electron energy loss spectroscopy as well as with angle-resolved two-photon photoemission and ultraviolet photoemission spectroscopy. In the sub-monolayer regime 8T adopts a flat-lying adsorption geometry. Upon reaching the monolayer coverage the orientation of 8T molecules changes towards a tilted configuration, with the long molecular axis parallel to the surface plane, facilitating attractive intermolecular π-π-interactions. The photoemission intensity from the highest occupied molecular orbitals (HOMO and HOMO - 1) possesses a strong dependence on the adsorption geometry due to the direction of the involved transition dipole moment for the respective photoemission process. The change in molecular orientation as a function of coverage in the first molecular layer mirrors the delicate balance between intermolecular and molecule/substrate interactions. Fine tuning of these interactions opens up the possibility to control the molecular structure and accordingly the desirable functionality.     

On ≤k-Edges, Crossings, and Halving Lines of Geometric Drawings of K n

Let P be a set of points in general position in the plane. Join all pairs of points in P with straight line segments. The number of segment-crossings in such a drawing, denoted by $\operatorname {cr}(P)$ , is the rectilinear crossing number of P. A halving line of P is a line passing through two points of P that divides the rest of the points of P in (almost) half. The number of halving lines of P is denoted by h(P). Similarly, a k-edge, 0??k??n/2?1, is a line passing through two points of P and leaving exactly k points of P on one side. The number of ??k-edges of P is denoted by E _??k (P). Let $\overline {\mathrm {cr}}(n)$ , h(n), and E _??k (n) denote the minimum of $\operatorname {cr}(P)$ , the maximum of h(P), and the minimum of E _??k (P), respectively, over all sets P of n points in general position in the plane. We show that the previously best known lower bound on E _??k (n) is tight for k<?(4n?2)/9? and improve it for all k???(4n?2)/9?. This in turn improves the lower bound on $\overline {\mathrm {cr}}(n)$ from $0.37968\binom{n}{4}+\varTheta (n^{3})$ to $\frac{277}{729}\binom{n}{4}+\varTheta (n^{3})\geq 0.37997\binom{n}{4}+\varTheta (n^{3})$ . We also give the exact values of $\overline {\mathrm {cr}}(n)$ and h(n) for all n??27. Exact values were known only for n??18 and odd n??21 for the crossing number, and for n??14 and odd n??21 for halving lines.     

Biological Risk Assessment of Three Dental Composite Materials following Gas Plasma Exposure

Gas plasma is an approved technology that generates a plethora of reactive oxygen species, which are actively applied for chronic wound healing. Its particular antimicrobial action has spurred interest in other medical fields, such as periodontitis in dentistry. Recent work has indicated the possibility of performing gas plasma-mediated biofilm removal on teeth. Teeth frequently contain restoration materials for filling cavities, e.g., resin-based composites. However, it is unknown if such materials are altered upon gas plasma exposure. To this end, we generated a new in-house workflow for three commonly used resin-based composites following gas plasma treatment and incubated the material with human HaCaT keratinocytes in vitro. Cytotoxicity was investigated by metabolic activity analysis, flow cytometry, and quantitative high-content fluorescence imaging. The inflammatory consequences were assessed using quantitative analysis of 13 different chemokines and cytokines in the culture supernatants. Hydrogen peroxide served as the control condition. A modest but significant cytotoxic effect was observed in the metabolic activity and viability after plasma treatment for all three composites. This was only partially treatment time-dependent and the composites alone affected the cells to some extent, as evident by differential secretion profiles of VEGF, for example. Gas plasma composite modification markedly elevated the secretion of IL6, IL8, IL18, and CCL2, with the latter showing the highest correlation with treatment time (Pearson’s r > 0.95). Cell culture media incubated with gas plasma-treated composite chips and added to cells thereafter could not replicate the effects, pointing to the potential that surface modifications elicited the findings. In conclusion, our data suggest that gas plasma treatment modifies composite material surfaces to a certain extent, leading to measurable but overall modest biological effects.     

Orbital and spin effects in the low-temperature behavior of the magnetoresistance of doped CdTe crystals

An observation of the suppression of negative magnetoresistance in samples of doped CdTe that are far from the metal-insulator transition as the temperature is lowered in the temperature range 3–0.4 K was previously reported [N. V. Agrinskaya, V. I. Kozub, and D. V. Shamshur, JETP 80, 1142 (1995)]. The results of an investigation of samples that are closer to the transition in the low-temperature region below 36 mK are presented. It is discovered that the samples investigated (which do not exhibit the suppression of negative magnetoresistance at comparatively high temperatures) display this effect at low temperatures and that, as previously, the suppression of the negative magnetoresistance correlates with the transition to conduction via Coulomb-gap states. A plateau-like magnetoresistance feature is displayed at low temperatures for the sample that is closest to the metal-insulator transition. The results obtained are analyzed within existing theoretical models that take into account the role of both the orbital and spin degrees of freedom. In particular, the low-temperature feature indicated is interpreted as a manifestation of positive magnetoresistance caused by spin effects. Nevertheless, it is shown within a detailed analysis supplemented by numerical calculations that the observed suppression of the negative magnetoresistance cannot be attributed only to the appearance of spin positive magnetoresistance. Moreover, the possibility of observing spin positive magnetoresistance is determined to a certain extent specifically by the suppression of the negative magnetoresistance competing with it. Zh. éksp. Teor. Fiz. 111, 1477–1493 (April 1997)     

Asymmetric Reductive Carbocyclization Using Engineered Ene Reductases

Ene reductases from the Old Yellow Enzyme (OYE) family reduce the C=C double bond in α,β‐unsaturated compounds bearing an electron‐withdrawing group, for example, a carbonyl group. This asymmetric reduction has been exploited for biocatalysis. Going beyond its canonical function, we show that members of this enzyme family can also catalyze the formation of C?C bonds. α,β‐Unsaturated aldehydes and ketones containing an additional electrophilic group undergo reductive cyclization. Mechanistically, the two‐electron‐reduced enzyme cofactor FMN delivers a hydride to generate an enolate intermediate, which reacts with the internal electrophile. Single‐site replacement of a crucial Tyr residue with a non‐protic Phe or Trp favored the cyclization over the natural reduction reaction. The new transformation enabled the enantioselective synthesis of chiral cyclopropanes in up to >99 % ee.     

A new critical point in the non-linear conductivity due to variable range hopping in Si

A critical point in the non-linear conductivity has been observed in epitaxial silicon in the variable range hopping regime, due to a negative differential resistance with a dc bias currentI _dc. This gives thermal breakdown via the electron-phonon coupling and circuit-limited oscillations with a frequencyf∝I _dc, below a critical temperatureT _c. This critical behaviour is intrinsic, and forR(T)=R ₀ exp(T ₀ /T)^1/2 we show thatT _c=0.00512T ₀.     

Supramolecular triads bearing porphyrin and fullerene via ‘two-point’ binding involving coordination and hydrogen bonding

Supramolecular triads composed of fullerene (C₆₀) as primary electron acceptor, zinc porphyrin (ZnP) as primary electron donor, and either a ferrocene (Fc), or N,N-dimethylaminophenyl (DMA), or N,N-diphenylaminophenyl (DPA) entity as a second electron donor were constructed via a ‘two-point’ binding motif involving axial coordination and hydrogen bonding. The B3LYP/3-21G(*) optimized structures revealed disposition of the three entities of the triads in a triangular fashion. The redox behavior of the different components was studied using cyclic voltammetry in o-dichlorobenzene containing 0.1 M (n-C₄H₉)₄NClO₄. The oxidation potentials of the second electron donor followed the trend: Fc<DMA<DPA, and the free-energy calculations suggested the possibility of the occurrence of sequential hole transfer in these triads. Efficient electron transfer from the excited singlet state of zinc porphyrin to the fullerene entity was observed in all of the studied triads in o-dichlorobenzene. Longer charge-separated states were observed for zinc porphyrin with a carboxylic acid compared with that having an amide group. The ratios of the experimentally determined forward to reverse electron transfer rates, k_CS/k_CR were evaluated to be 10³ for triads formed by zinc porphyrin with a carboxylic acid, suggesting charge stabilization in these triads.     

Disodium guanosine 5'-monophosphate self-associates into nanoscale cylinders at pH 8: a combined diffusion NMR spectroscopy and dynamic light scattering study

We report a combined NMR and dynamic light scattering (DLS) study on the size of supramolecular structures formed by disodium guanosine 5'-monophosphate, Na(2)(5'-GMP), at pH 8. In general, two distinct types of aggregate species are present in an aqueous solution of Na(2)(5'-GMP). One type consists of stacking 5'-GMP monomers, and the other contains stacking G-quartets. Both types of aggregates can be modeled as rodlike cylinders. The cylinder diameter is 10 and 26 A for monomer aggregates and quartet aggregates, respectively. For Na(2)(5'-GMP) concentrations between 18 and 34 wt %, the cylinders formed by stacking G-quartets have an average length between 8 and 30 nm, corresponding to a stack of approximately 24-87 G-quartets. These nanoscale aggregates are significantly larger than what had previously been believed for Na(2)(5'-GMP) self-association at pH 8. The length of both types of 5'-GMP aggregates was found to increase with Na(2)(5'-GMP) concentration but was insensitive to the added NaCl in solution. While the aggregate size for monomer aggregates increases with a decrease in temperature, the size of G-quartet aggregates is essentially independent of temperature. We found that the size of G-quartet aggregates is slightly larger in D(2)O than in H(2)O, whereas the size of monomer aggregates remains the same in D(2)O and in H(2)O. We observed a linear relationship between the axial ratio of the 5'-GMP cylinders and the Na(2)(5'-GMP) concentration for both types of 5'-GMP aggregates, which suggests a common stacking mechanism for monomers and G-quartets.