Two-Dimensional Supramolecular Polymerization of a Bis-Urea Macrocycle into a Brick-Like Hydrogen-Bonded Network

We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl₃ or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development.     

Effect of trifluoroacetic acid upon Boc-aminoacyl- and Box-peptidyl-resins. Description of a new polymeric support for solid phase peptide synthesis.

The behavior of Boc-aminoacyl- and Boc-peptidyl-OCH₂-resins towards TFA/CH₂Cl₂ solutions has been studied. The results obtained point out the difficulty of finding an optimum TFA concentration which achieves total deprotection without substantial acidolytic losses. The synthesis of a new polymeric support which minimizes this problem is described.     

Triphase vs. two-phase transfer catalysis: an eclectic approach

A new and effective way of eliminating phase transfer catalysts from an organic phase involves treatment with an ion exchange resin in a triphase system.     

Generalized time-dependent density-functional theory including core polarization

A generalization of the time-dependent density-functional-theory for metal clusters which treats both valence and core polarization on the same microscopic basis is presented. The selfconsistency between valence and core responses is taken into account by means of a modified kernel and external field in the linearized response equations. The general case of an arbitrary external field and cluster structure, with given specific atomic positions, is presented. Presented by Ll. Serra at the International Conference on “Atomic Nuclei and Metallic Clusters”, Prague, September 1–5, 1997.     

13C/12C isotope labeling to study carbon partitioning and dark respiration in cereals subjected to water stress

Despite the relevance of carbon (C) loss through respiration processes (with its consequent effect on the lower C availability for grain filling), little attention has been given to this topic. Literature data concerning the role of respiration in cereals are scarce and these have been produced using indirect methods based on gas‐exchange estimations. We have developed a new method based on the capture of respired CO₂ samples and their analysis by gas chromatography‐combustion‐isotope ratio mass spectrometry (GC‐C‐IRMS). In order to analyse the main processes involved in the C balance during grain filling (photosynthesis, respiration, allocation and partitioning) the ambient isotopic ¹³C/¹²C composition (δ¹³C) of the growth chamber was modified during this period (δ¹³C ca. ?12.8 ± 0.3‰ to ca. ?20.0 ± 0.2‰). The physiological performance, together with the C allocation on total organic matter (TOM) and respiration of wheat (Triticum aestivum L., var. Califa sur) and two hybrids, tritordeum (X Tritordeum Asch. & Graebn line HT 621) and triticale (X Triticosecale Wittmack var. Imperioso), were compared during post‐anthesis water stress. In spite of the larger ear DM/total ratio, especially under drought conditions, the grain filling of triticale and wheat was mainly carried out with pre‐anthesis C, while the majority of C assimilated during post‐anthesis was invested in respiration processes. In the case of wheat and tritordeum, the C balance data suggested a reallocation during grain filling of photoassimilates stored prior to anthesis from shoot to ear. Furthermore, the lower percentage of labeled C on respired CO₂ of droughted tritordeum plants, together with the lower plant biomass, explained the fact that those plants had more C available for grain filling. Copyright © 2009 John Wiley & Sons, Ltd.     

Micellar liquid chromatography determination of B vitamins with direct injection and ultraviolet absorbance detection

A micellar reversed-phase liquid chromatographic procedure was developed for the control of five water-soluble vitamins, B (nicotinamide), B1 (thiamine), B2 (riboflavin), B6 (pyridoxine and pyridoxamine), in multivitamin pharmaceutical formulations (capsules, pills and syrups). Optimization procedure includes studies about the composition of the mobile phase (sodium dodecyl sulphate and the modifiers propanol, butanol or pentanol), flow-rate and temperature. Chromatographic analysis of all vitamins was carried out using a single mobile phase of 0.1 M SDS-4% (v/v) pentanol at pH 3, in a C18 column in isocratic mode, and UV-detection at 270, 290 and 325 nm. The flow-rates selected were 1.0 ml/min in the interval 0 to 6 min, and 2.0 ml/min until the end of the chromatogram and temperature was 45 degrees C. In the micellar liquid chromatographic system, the samples were injected without pretreatment, and the analysis time was below 12 min. Repeatabilities and intermediate precision were achieved according to ICH, and were below 5%. When the method is applied to real samples, the amount found with respect to the declared compositions were within the 91-105% range. These results were similar to those obtained with a conventional 60:40 (v/v) methanol-water mixture for some of the vitamins, but with the advantage of use a single mobile phase for the analyses of the five vitamins, with direct injection of the samples and reduced toxicity, flammability, environmental impact and cost of the micellar-pentanol solutions.     

Sum Rules for the spin surface response of metal clusters within the time dependent local spin density approximation

We study surface spin collective modes of simple metallic clusters using a sum rule approach. We derive analytical expressions for the energy and cubic energy-weighted moments of the time-dependent local-spin-density approximation (TDLSDA) strength function. With these two moments we obtain a mean excitation energy of multipole spin modes and study its dispersion with cluster size up to very large sizes. The crucial roles played by the surface diffuseness and by correlation and kinetic energy effects on the resonance energies are stressed.     

Collective excitations of embedded potassium clusters

The collective surface-plasmon excitation of potassium clusters embedded in different dielectric matrices has been studied within the time-dependent local-density-approximation and the jellium model. The matrix has been taken into account through a static dielectric constant in both the cluster ground state and in the determination of the dynamical susceptibility. We conclude that the change in the residual electron-electron interaction when the cluster is introduced in a matrix is a basic effect for the determination of the static polarizabilities and plasma frequencies. As we increase the surface-plasmon energy is shifted to the red and a tendency to saturation is obtained. The red shift is in good agreement with electron-energy-loss spectroscopy experiments.     

Optical response of Ag clusters

The dielectric model proposed by Liebsch is solved for Ag clusters within time dependent density functional theory. The distribution of oscillator strength is analyzed and departures from the behaviour of simple (alkali) clusters are stressed. Comparison with experimental results of isolated Ag _N ⁺ clusters is made. The observed blueshift as the size of the cluster decreases is explained by a reduction of the s-d screening interaction in the surface region. As a microscopic justification of the model, the response of the Ag⁺ core is calculated using the embedded atom approximation.