Structure of the phonon sidebands in the t1 → s0 transition of naphthalene in p-dibromobenzene, α-phase p-dichlorobenzene,and γ-phase p-dichlorobenzene host crystals

The theory used for predicting the intensity distributions in phonon sidebands in the electronic spectra of molecular crystals is briefly reviewed with particular emphasis on chemically mixed crystals. Criteria are suggested for the identification of pseudolocalized features in phonon sidebands. The phonon sidebands associated with the phosphorescence of naphthalene in p-dibromobenzene and α-phase p-dichlorobenzene seem to exhibit some degree of localization, while the phonon sideband of the phosphorescence of naphthalene in γ-phase p-dichlorobenzene appears to be entirely delocalized. The results are compared with those of other workers and a correlation is established between the degree of localization and the strength of the exciton-phonon coupling as measured by the optical Debye-Waller factor. It is further shown that the strength of coupling of the phonons to the electronic transition is independent of the gas-to-crystal shift of the impurity.     

Solid-supported synthesis of a peptide beta-turn mimetic

[structure: see text]The solid-supported synthesis of a bicyclic diketopiperazine, a potential peptide beta-turn mimetic, is described. The Ugi reaction between the resin ester of alpha-N-Boc-diaminopropionic acid (an amine input), alpha-bromo acid, aldehyde, and isocyanide is the key step in the proposed protocol.     

Triplex and quadruplex DNA structures studied by electrospray mass spectrometry

DNA triplex and quadruplex structures have been successfully detected by electrospray ionization mass spectrometry (ESI-MS). Circular dichroism and UV-melting experiments show that these structures are stable in 150 mM ammonium acetate at pH 7 for the quadruplexes and pH 5.5 for the triplexes. The studied quadruplexes were the tetramer [d(TGGGGT)](4), the dimer [d(GGGGTTTTGGGG)](2), and the intramolecular folded strand dGGG(TTAGGG)(3), which is an analog of the human telomeric sequence. The absence of sodium contamination allowed demonstration of the specific inclusion of n - 1 ammonium cations in the quadruplex structures, where n is the number of consecutive G-tetrads. We also detected the complexes between the quadruplexes and the quadruplex-specific drug mesoporphyrin IX. MS/MS spectra of [d(TGGGGT)](4) and the complex with the drug are also reported. As the drug does not displace the ammonium cations, one can conclude that the drug binds at the exterior of the tetrads, and not between them. For the triplex structure the ESI-MS spectra show the detection of the specific triplex, at m/z values typically higher than those typically observed for duplex species. Upon MS/MS the antigene strand, which is bound into the major groove of the duplex, separates from the triplex. This is the same dissociation pathway as in solution. To our knowledge this is the first report of a triplex DNA structure by electrospray mass spectrometry.     

Distinguishing Ontario ginseng landraces and ginseng species using NMR-based metabolomics

The use of ¹H-NMR-based metabolomics to distinguish and identify unique markers of five Ontario ginseng (Panax quinquefolius L.) landraces and two ginseng species (P. quinquefolius and P. ginseng) was evaluated. Three landraces (2, 3, and 5) were distinguished from one another in the principal component analysis (PCA) scores plot. Further analysis was conducted and specific discriminating metabolites from the PCA loadings were determined. Landraces 3 and 5 were distinguishable on the basis of a decreased NMR intensity in the methyl ginsenoside region, indicating decreased overall ginsenoside levels. In addition, landrace 5 was separated by an increased amount of sucrose relative to the rest of the landraces. Landrace 2 was separated from the rest of the landraces by the increased level of ginsenoside R_b1. The Ontario P. quinquefolius was also compared with Asian P. ginseng by PCA, and clear separation between the two groups was detected in the PCA scores plot. The PCA loadings plot and a t-test NMR difference plot were able to identify an increased level of maltose and a decreased level of sucrose in the Asian ginseng compared with the Ontario ginseng. An overall decrease of ginsenoside content, especially ginsenoside R_b1, was also detected in the Asian ginseng’s metabolic profile. This study demonstrates the potential of NMR-based metabolomics as a powerful high-throughput technique in distinguishing various closely related ginseng landraces and its ability to identify metabolic differences from Ontario and Asian ginseng. The results from this study will allow better understanding for quality assessment, species authentication, and the potential for developing a fully automated method for quality control.

Ketopiperazines: Conformationally Constrained Peptidomimetic of Arginine Amides

We have synthesized guanidine‐containing ketopiperazines designed to be conformational mimics of peptidomimetic arginine amides. D‐Allylglycine was converted by an efficient approach to give enantiopure ketopiperazines in which the trans stereochemistry of the C‐substituents resulted from stereospecific enolate alkylation.     

Microwave-Assisted Desulfation of the Hemolytic Saponins Extracted from Holothuria scabra Viscera

Saponins are plant and marine animal specific metabolites that are commonly considered as molecular vectors for chemical defenses against unicellular and pluricellular organisms. Their toxicity is attributed to their membranolytic properties. Modifying the molecular structures of saponins by quantitative and selective chemical reactions is increasingly considered to tune the biological properties of these molecules (i) to prepare congeners with specific activities for biomedical applications and (ii) to afford experimental data related to their structure–activity relationship. In the present study, we focused on the sulfated saponins contained in the viscera of Holothuria scabra, a sea cucumber present in the Indian Ocean and abundantly consumed on the Asian food market. Using mass spectrometry, we first qualitatively and quantitatively assessed the saponin content within the viscera of H. scabra. We detected 26 sulfated saponins presenting 5 different elemental compositions. Microwave activation under alkaline conditions in aqueous solutions was developed and optimized to quantitatively and specifically induce the desulfation of the natural saponins, by a specific loss of H₂SO₄. By comparing the hemolytic activities of the natural and desulfated extracts, we clearly identified the sulfate function as highly responsible for the saponin toxicity.     

On list primitive recursion and the complexity of computinginf

We present a primitive recursive programinf_with_lists computing the minimum of two natural numbersn andp (written in unary notation) and using primitive recursion on lists. This program has at first sight the required property of visiting simultaneously its inputs, so it is a counterexample to a theorem showing that such a program cannot be written in the language of primitive recursion on natural numbers, in the more general framework of primitive recursion on term algebras. However, its complexity is at leastinf(n,p)² so it does not implement the algorithm we have in mind to computeinf(n,p).     

Vortex fluctuations in underdoped Bi(2)Sr(2)CaCu(2)O(8+delta) crystals

Vortex thermal fluctuations in heavily underdoped Bi(2)Sr(2)CaCu(2)O(8+delta) (T(c)=69.4 K) are studied using Josephson plasma resonance. From the zero-field data, we obtain the c-axis penetration depth lambda(L,c)(0)=230+/-10 micrometer and the anisotropy ratio gamma(T). The low plasma frequency allows us to study phase correlations over the whole vortex solid state and to extract a wandering length r(w) of vortex pancakes. The temperature dependence of r(w) as well as its increase with dc magnetic field is explained by the renormalization of the vortex line tension by the fluctuations, suggesting that this softening is responsible for the dissociation of the vortices at the first order transition.     

Vortex pinning: A probe for nanoscale disorder in iron-based superconductors

The pinning of quantized flux lines, or vortices, in the mixed state is used to quantify the effect of impurities in iron-based superconductors (IBS). Disorder at two length scales is relevant in these materials. Strong flux pinning resulting from nm-scale heterogeneity of the superconducting properties leads to the very disordered vortex ensembles observed in the IBS, and to the pronounced maximum in the critical current density j_c at low magnetic fields. Disorder at the atomic scale, most likely induced by the dopant atoms, leads to “weak collective pinning” and a magnetic field-independent contribution j_c^coll. The latter allows one to estimate quasiparticle scattering rates.     

Experimental design applied to spin coating of 2D colloidal crystal masks: a relevant method?

Monolayers of colloidal spheres are used as masks in nanosphere lithography (NSL) for the selective deposition of nanostructured layers. Several methods exist for the formation of self-organized particle monolayers, among which spin coating appears to be very promising. However, a spin coating process is defined by several parameters like several ramps, rotation speeds, and durations. All parameters influence the spreading and drying of the droplet containing the particles. Moreover, scientists are confronted with the formation of numerous defects in spin coated layers, limiting well-ordered areas to a few micrometers squared. So far, empiricism has mainly ruled the world of nanoparticle self-organization by spin coating, and much of the literature is experimentally based. Therefore, the development of experimental protocols to control the ordering of particles is a major goal for further progress in NSL. We applied experimental design to spin coating, to evaluate the efficiency of this method to extract and model the relationships between the experimental parameters and the degree of ordering in the particles monolayers. A set of experiments was generated by the MODDE software and applied to the spin coating of latex suspension (diameter 490 nm). We calculated the ordering by a homemade image analysis tool. The results of partial least squares (PLS) modeling show that the proposed mathematical model only fits data from strictly monolayers but is not predictive for new sets of parameters. We submitted the data to principal component analysis (PCA) that was able to explain 91% of the results when based on strictly monolayered samples. PCA shows that the ordering was positively correlated to the ramp time and negatively correlated to the first rotation speed. We obtain large defect-free domains with the best set of parameters tested in this study. This protocol leads to areas of 200 μm(2), which has never been reported so far.