A theoretical study of special acoustic effects caused by the staircase of the El Castillo pyramid at the Maya ruins of Chichen-Itza in Mexico

It is known that a handclap in front of the stairs of the great pyramid of Chichen Itza produces a chirp echo which sounds more or less like the sound of a Quetzal bird. The present work describes precise diffraction simulations and attempts to answer the critical question what physical effects cause the formation of the chirp echo. Comparison is made with experimental results obtained from David Lubman. Numerical simulations show that the echo shows a strong dependence on the kind of incident sound. Simulations are performed for a (delta function like) pulse and also for a real handclap. The effect of reflections on the ground in front of the pyramid is also discussed. The present work also explains why an observer seated on the lowest step of the pyramid hears the sound of raindrops falling in a water filled bucket instead of footstep sounds when people, situated higher up the pyramid, climb the stairs.     

Crystal structure of Mg2(OH)2CO3, deduced from the topotactic thermal decomposition of artinite

By means of single-crystal X-ray diffraction of nondecomposed, partly, and fully decomposed artinite (Mg₂(OH)₂CO₃·3H₂O), it has been shown that the intermediate product of decomposition, Mg₂(OH)₂CO₃, is not amorphous. Its unit cell has been determined and a model of its structure has been deduced, which can account for both the lattice parameters and the relative orientations of the unit cells of artinite, intermediate product, and magnesium oxide found experimentally. The decomposition reaction can be described as a topotactic process with conservation of chains in both and additional conservation of layers in the second step.     

Aluminacyclopropene: syntheses, characterization, and reactivity toward terminal alkynes

Reactions of LAl with ethyne, mono- and disubstituted alkynes, and diyne to aluminacyclopropene LAl[eta2-C2(R1)(R2)] ((L = HC[(CMe)(NAr)]2, Ar = 2,6-iPr2C6H3); R1 = R2 = H, (1); R1 = H, R2 = Ph, (2); R1 = R2 = Me, (3); R1 = SiMe3, R2 = C[triple bond]CSiMe3, (4)) are reported. Compounds 1 and 2 were obtained in equimolar quantities of the starting materials at low temperature. The amount of C2H2 was controlled by removing an excess of C2H2 in the range from -78 to -50 degrees C. Compound 4 can be alternatively prepared by the substitution reaction of LAl[eta2-C2(SiMe3)2] with Me3SiC[triple bond]CC[triple bond]CSiMe3 or by the reductive coupling reaction of LAlI2 with potassium in the presence of Me3SiC[triple bond]CC[triple bond]CSiMe3. The reaction of LAl with excess C2H2 and PhC[triple bond]CH (<1:2) afforded the respective alkenylalkynylaluminum compounds LAl(CH=CH2)(C[triple bond]CH) (5) and LAl(CH=CHPh)(C[triple bond]CPh) (6). The reaction of LAl(eta2-C2Ph2) with C2H2 and PhC[triple bond]CH yielded LAl(CPh=CHPh)(C[triple bond]CH) (7) and LAl(CPh=CHPh)(C[triple bond]CPh) (8), respectively. Rationally, the formation of 5 (or 6) may proceed through the corresponding precursor 1 (or 2). The theoretical studies based on DFT calculations show that an interaction between the Al(I) center and the C[triple bond]C unit needs almost no activation energy. Within the AlC2 ring the computational Al-C bond order of ca. 1 suggests an Al-C sigma bond and therefore less pi electron delocalization over the AlC2 ring. The computed Al-eta2-C2 bond dissociation energies (155-82.6 kJ/mol) indicate a remarkable reactivity of aluminacyclopropene species. Finally, the 1H NMR spectroscopy monitored reaction of LAl(eta2-C2Ph2) and PhC[triple bond]CH in toluene-d8 may reveal an acetylenic hydrogen migration process.     

Quantitative Depth Profiling of K-Doped Fullerene Films Using XPS and SIMS

 Phenomena accompanying electrochemical doping of solid fullerene films with potassium were studied by sputter ion depth profiling (XPS and SIMS). The potassium distribution was determined, and artifacts associated with possible damage of the layer composition caused by ion impact were investigated and discussed. To compare the charge transfer while reductive doping is taking place at fullerene/solution interface with doping from gas phase, model layers were prepared and doped by potassium under UHV conditions. It was found that sputtering by Ar⁺ primary ions yields both accurate information on the alkaline metal distribution and on its concentration. Sputtering by O⁺ ions led to an enrichment of potassium, apparently due to the reactivity of oxygen with the fullerene matrix. It is shown that the reductive doping starts at the fullerene/solution interface. The concentration of potassium in the doped films was found to be lower than expected from the charge transferred during the electrochemical reduction. Other phase transformations such as hydrogenation are discussed. Received March 4, 2002; accepted July 26, 2002     

3β‐Acetoxy‐5α,6β‐di­hydroxybisnorcholanic acid 2216 lactone

In the title compound, C₂₄H₃₆O₆, the ester linkage in ring A is equatorial. The six‐membered rings A, B and C have chair conformations. The five‐membered ring D adopts a 13β,14α‐half‐chair conformation and the E ring adopts an envelope conformation. The A/B, B/C and C/D ring junctions are trans, whereas the D/E junction is cis.     

The Diversity of a Polyclonal FluCell-SELEX Library Outperforms Individual Aptamers as Emerging Diagnostic Tools for the Identification of Carbapenem Resistant Pseudomonas aeruginosa

Textbook procedures require the use of individual aptamers enriched in SELEX libraries which are subsequently chemically synthesized after their biochemical characterization. Here we show that this reduction of the available sequence space of large libraries and thus the diversity of binding molecules reduces the labelling efficiency and fidelity of selected single aptamers towards different strains of the human pathogen Pseudomonas aeruginosa compared to a polyclonal aptamer library enriched by a whole-cell-SELEX involving fluorescent aptamers. The library outperformed single aptamers in reliable and specific targeting of different clinically relevant strains, allowed to inhibit virulence associated cellular functions and identification of bound cell surface targets by aptamer based affinity purification and mass spectrometry. The stunning ease of this FluCell-SELEX and the convincing performance of the P. aeruginosa specific library may pave the way towards generally new and efficient diagnostic techniques based on polyclonal aptamer libraries not only in clinical microbiology.     

Photoconvertible fluorescent protein EosFP: biophysical properties and cell biology applications

EosFP is a fluorescent protein from the coral Lobophyllia hemprichii that changes its fluorescence emission from green to red upon irradiation with near-UV light. Here we present the spectroscopic properties of wild-type EosFP and a variety of monomeric and dimeric mutants and provide a structural interpretation of its oligomerization and photoconversion, which is based on X-ray structure analysis of the green and red species that we reported recently. Because functional expression of the monomeric EosFP variant is limited to temperatures of 30 degrees C, we have developed a tandem dimer. This construct, in which two EosFP subunits are connected by a flexible 12 amino acid linker, expresses well after fusion with the androgen and endothelin A receptors at 37 degrees C. A variety of applications in cellular imaging, developmental biology and automated high-content screening applications are presented, which demonstrate that EosFP is a powerful tool for in vivo monitoring of cellular processes.     

Explicitly correlated coupled cluster calculations for the benzenium ion (C6H7(+)) and its complexes with Ne and Ar

Explicitly correlated coupled cluster theory at the CCSD(T)-F12x (x = a, b) level (Adler, T. B.; Knizia, G.; Werner, H.-J. J. Chem. Phys. 2007, 127, 221106) has been employed in a study of the benzenium ion (C6H7(+)) and its complexes with a neon or an argon atom. The ground-state rotational constants of C6H7(+) are predicted to be A0 = 5445 MHz, B0 = 5313 MHz, and C0 = 2731 MHz. Anharmonic vibrational wavenumbers of this cation were obtained by combination of harmonic CCSD(T*)-F12a values with anharmonic contributions calculated by double-hybrid density functional theory at the B2PLYP-D level. For the complexes of C6H7(+) with Ne or Ar, the lowest energy minimum is of π-bonded structure. The corresponding dissociation energies D0 are estimated to be 160 and 550 cm(-1), respectively. There is no indication of H-bonds to the aromatic or aliphatic hydrogen atoms. Instead, three nonequivalent local energy minima were found for nuclear configurations where the rare-gas atom lies in the ring-plane and approximatly points to the center of one of the six CC bonds.     

XPS investigations of electrolyte/electrode interactions for various Li-ion battery materials

For future Li-ion battery applications the search for both new design concepts and materials is necessary. The electrodes of the batteries are always in contact with electrolytes, which are responsible for the transport of Li ions during the charging and discharging process. A broad range of materials is considered for both electrolytes and electrodes so that very different chemical interactions between them can occur, while good cycling behavior can only be obtained for stable solid-electrolyte interfaces. X-ray photoelectron spectroscopy (XPS) was used to study the most relevant interactions between various electrode materials in contact with different electrolyte solutions. It is shown how XPS can provide useful information on reactivities and thus preselect suitable electrode/electrolyte combinations, prior to electrochemical performance tests.