Synthesis of des-n-tetramethyltriostin a from C-terminal Z-d-serine tetra-and octadepsipeptide intermediates

Des-N-tetramethyltriostin A (1), a known DNA-intercalation agent, has been synthesized from tetra- and octapeptide intermediates that have Z-d-serine at the C-terminal position. The procedure thus allows the fragment coupling and cyclization reactions leading to the synthesis of the title compound to occur without racemization at the C-terminal amino acid. Esterification of Boc-Val-OH with the p-bromophenacyl ester of Z-d-serine provided didepsipeptide Z-d-Ser(Boc-Val)-OBpa (4). Stepwise addition of the requisite amino acids provided tetradepsipeptide Z-d-Ser[Boc-Ala-Cys(Acm)-Val]-OBpa (6). Fragment coupling of the respective C- and N-deprotected tetradepsipeptides 7 and 8, derived from 6, furnished linear octadepsipeptide 9, which upon cyclization and disulfide formation gave the bicyclic octadepsipeptide 11, a known synthetic precursor to 1. The degree of racemization incurred in the alanine and valine residues of selected depsipeptides was measured and the results compared with those obtained in previous studies. It was concluded that alanine, perhaps because of sequence effects, undergoes a degree of racemization (4–10%) during hydrolysis of tetradepsipeptide 6 and octadepsipeptide 9.     

Instantaneous frequency decomposition: an application to spectrally sparse sounds with fast frequency modulations

Classical time-frequency analysis is based on the amplitude responses of bandpass filters, discarding phase information. Instantaneous frequency analysis, in contrast, is based on the derivatives of these phases. This method of frequency calculation is of interest for its high precision and for reasons of similarity to cochlear encoding of sound. This article describes a methodology for high resolution analysis of sparse sounds, based on instantaneous frequencies. In this method, a comparison between tonotopic and instantaneous frequency information is introduced to select filter positions that are well matched to the signal. Second, a cross-check that compares frequency estimates from neighboring channels is used to optimize filter bandwidth, and to signal the quality of the analysis. These cross-checks lead to an optimal time-frequency representation without requiring any prior information about the signal. When applied to a signal that is sufficiently sparse, the method decomposes the signal into separate time-frequency contours that are tracked with high precision. Alternatively, if the signal is spectrally too dense, neighboring channels generate inconsistent estimates-a feature that allows the method to assess its own validity in particular contexts. Similar optimization principles may be present in cochlear encoding.     

Novel coexistence of superconductivity with two distinct magnetic orders

The heavy fermion system exhibits properties that range from an incommensurate antiferromagnet for small to an exotic superconductor on the Ir-rich end of the phase diagram. At intermediate where antiferromagnetism coexists with superconductivity, two types of magnetic order are observed: the incommensurate one of and a new, commensurate antiferromagnetism that orders separately. The coexistence of -electron superconductivity with two distinct -electron magnetic orders is unique among unconventional superconductors, adding a new variety to the usual coexistence found in magnetic superconductors.     

Unprecedented oxo-titanium citrate complex precipitated from aqueous citrate solutions, exhibiting a novel bilayered Ti8O10 structural core

Aqueous titanium citrate solutions were prepared from the reaction of citric acid with titanium 2-propoxide in a range of molar ratios. Solutions containing two or fewer citrates per titanium resulted in the slow crystallization of an insoluble titanium oxo-citrate complex. Single-crystal X-ray analysis identified the species as Ti(8)O(10)(citrate)(4)(H(2)O)(12).14H(2)O.3HOPr(i)(), crystallized in the tetragonal space group I4(1)/a, with a = 30.775(7) A, c = 14.528(7) A, V = 13 759(8) A(3), and Z = 8. The trianionic citrate ligands supply both carboxylate and alkoxide coordination and stabilize the structure using simultaneous chelating and bridging modes of attachment. The compound is a neutral species, exhibiting titanium in three contrasting environments. Laser Raman microscopy and (13)C CPMAS solid-state NMR data were consistent with those of the X-ray crystal structure. When exposed to air, the crystals rapidly lost water and became a powder. The dehydrated powder was noncrystalline to X-rays and insoluble, but (13)C NMR results demonstrated retention of the carboxylate linkages.     

Proton transfer versus redox modulation in thiourea-phenanthrenequinone molecular and polymeric complexes

Phenanthrenequinone undergoes highly efficient proton transfer processes in the presence of a thiourea-functionalised polystyrene copolymer whereas interactions with a similar benzyl-thiourea monomer show strong redox modulation of the quinone without proton transfer.     

Multiple time scale simulations of metal crystal growth reveal the importance of multiatom surface processes

A method for extending atomistic computer simulations of solids beyond the nanosecond time scale was used to simulate metal crystal growth on the time scale of laboratory experiments. Transitions involving concerted motion of multiple atoms on the crystal surface are found to lead to remarkably smooth growth of pure Al(100). Cu(100) is found to grow with a rougher surface, consistent with experiments. Not only is the activation energy of the multiatom Al processes surprisingly low, but vibrational entropy also favors processes where many atoms are displaced.     

Electrochemically tuneable hydrogen bonding interactions between a phenyl-urea terminated dendrimer and phenanthrenequinone

Electrochemically tuneable hydrogen bonding interactions are described between a phenyl-urea terminated dendrimer and phenanthrenequinone.     

Model systems for flavoenzyme activity: relationships between cofactor structure, binding and redox properties

A series of flavins were synthesized bearing electron-withdrawing and -donating substituents. The electrochemical properties of these flavins in a nonpolar solvent were determined. The recognition of these flavins by a diamidopyridine (DAP) receptor and the effect this receptor has on flavin redox potential was also quantified. It was found that the DAP-flavin binding affinity and the reduction potentials (E(1/2)) for both the DAP-bound and unbound flavins correlated well with functions derived from linear free energy relationships (LFERs). These results provide insight and predictive capability for the interplay of electronics and redox state-specific interactions for both abiotic and enzymatic systems.     

Sound cancellation by the use of secondary multipoles: experiments

Theory related to global, free-field cancellation of a primary monopole field by the use of a displaced, secondary multipole was presented previously: a corresponding experimental investigation is presented here. The construction of multipole source components to octopole order is described, as are procedures for determining their source strengths. Dipoles, longitudinal quadrupoles, and longitudinal octopoles that conformed closely to their theoretical models were constructed using arrays of unbaffled loudspeakers. Two methods of calculating the multipole strengths required to cancel a primary monopole field were implemented in an open-loop manner: a "direct" approach based on a multipole expansion of the primary field, and a least-squares procedure based on fitting the secondary field to the primary field either along a circle enclosing a secondary source, or along a segment of that circle. Cancellation measurements were made on a 1-m-radius circle centered on the secondary source: the primary-to-secondary source separation was approximately 0.2 wavelengths. It was found both that a secondary multipole could provide far greater cancellation than a monopole placed at the same distance from the primary source and that the least-squares approach resulted in greater far-field cancellation than did the direct approach.     

An acoustic study of soils that model seabed sediments containing gas bubbles

The acoustic response of gassy seabed sediment is unique. It is a dispersive and extraordinarily attenuative natural material at frequencies which cause gas bubble resonance. It conceals the structure of the seabed from seismic profiling and it dampens acoustic signals that, for example, trigger acoustic mines. In the past, theoretical studies have formulated the probable cause of this response and crude experimental work has partially corroborated theory. This study measures compressional wave velocity and attenuation in a laboratory soil simulating natural gassy soil, and it investigates the structural properties that cause the unique acoustic response. It was confirmed that below the frequencies which cause resonance the soil behaves as a compressible material (containing gas), and above as a relatively incompressible material (containing no gas). Over the frequency range producing bubble resonance it is suggested that the soil should be modeled as a biphasic material of gas and a relatively incompressible saturated soil matrix (particles and fluid). Velocities for gassy soil were found to be as low as 220 m/s at frequencies below resonance and 1500 m/s above resonance; attenuations were found to be as high as 60 dB/cm for moderately gassy soil and as low as 1 dB/cm for soil with almost no gas.