Chemistry of renieramycins. Part 7: Renieramycins T and U, novel renieramycin-ecteinascidin hybrid marine natural products from Thai sponge Xestospongia sp.

Two new bistetrahydroisoquinoline marine natural products, renieramycins T (1) and U (2), were isolated from the Thai blue sponge Xestospongia sp. and their structures were elucidated by comparing spectral data with those of renieramycin M (3a) and ecteinascidin 770 (4a). These compounds are the first reported examples of novel ecteinascidin-renieramycin hybrid natural products. Renieramycin T (1) showed strong cytotoxicity to several human cancer cell lines, its IC₅₀ values ranging from 4.7 to 98 nM.     

Dynamics of Decision Making in Animal Group Motion

We analyze a continuous-time model of a multi-agent system motivated by simulation studies on dynamics of decision making in animal groups in motion. Each individual moves at constant speed in the plane and adjusts its heading in response to relative headings of others in the population. The population includes two subgroups that are “informed” such that individuals in each subgroup have a preferred direction of motion. The model exhibits fast and slow time scales allowing for a reduction in the dimension of the problem. The stable solutions for the reduced model correspond to compromise by individuals with conflicting preferences. We study the global phase space for the proposed reduced model by computing equilibria and exploring stability and bifurcations. B. Nabet’s and N.E. Leonard’s work is supported in part by AFOSR grant FA9550-07-1-0-0528 and ONR grants N00014-02-1-0826 and N00014-04-1-0534. I.D. Couzin’s work was supported by the Royal Society, Balliol College and EPSRC grants GR/S04765/01 and GR/T11234/01, a Searle Scholar Award and DARPA grant HR001-05-1-0057. S.A. Levin’s work was supported in part by DARPA grant HR0011-05-1-0057 and NSF grant EF-0434319.     

Dendritic folate rosettes as ion channels in lipid bilayers

The self-assembly of folate dendrimers into pi-stacked supramolecular rosettes is shown to produce ion channels in planar and spherical lipid bilayer membranes. The found ion channels are small, quite homogeneous, long-lived, ohmic, cation selective (Eisenman I), and blockable by the permeant cation.     

Analysis of lanthanide-induced NMR shifts of the Ce@C82 anion

The mapping of bond connectivity in the carbon cage of [Ce@C82]- and full assignment of the NMR lines were successfully achieved by means of 2D INADEQUATE NMR measurement. Paramagnetic NMR analysis shows that the Ce atom in [Ce@C82]- is located at an off-centered position adjacent to a hexagonal ring along the C2 axis of the C2v-C82 cage.     

Chemical understanding of carbide cluster metallofullerenes: a case study on Sc2C2@C2v(5)-C80 with complete X-ray crystallographic characterizations

Little is known about the chemical properties of carbide cluster metallofullerenes (CCMFs). Here we report the photochemical reaction of a newly assigned CCMF Sc(2)C(2)@C(2v)(5)-C(80) with 2-adamantane-2,3-[3H]-diazirine (AdN(2), 1), which provides a carbene reagent under irradiation. Five monoadduct isomers (2a-2e), with respective abundances of 20%, 40%, 25%, 5%, and 10%, were isolated and characterized with a combination of experimental techniques including unambiguous single-crystal X-ray crystallography. Results show that the two Sc atoms of the bent Sc(2)C(2) cluster tend to move in most cases, whereas the C(2)-unit is almost fixed. Accordingly, it is difficult to explain the addition patterns by considering the strain and charge density on the cage with a fixed cluster, and thus a moving cluster may account for the addition patterns. These results show that the situation of CCMFs is more complicated than those in other metallofullerenes. Furthermore, a thermal isomerization process from 2b to 2c was observed, confirming that the most abundant isomer 2b is a kinetically favored adduct. Finally, it is revealed that the electronic and electrochemical properties of pristine Sc(2)C(2)@C(2v)(5)-C(80) have been markedly altered by exohedral modification.     

Measurement of a pauli and orbital paramagnetic state in bulk gold using x-ray magnetic circular dichroism spectroscopy

We show that bulk gold (Au) exhibits temperature-independent paramagnetism in an external magnetic field by x-ray magnetic circular dichroism spectroscopy at the Au L(2) and L(3) edges. Using the sum-rule analysis, we obtained a magnetic moment of 1.3 × 10(-4) μB/atom in an external magnetic field of 10 T and a paramagnetic susceptibility of 8.9 × 10(-6) for the 5d orbit. The induced paramagnetism in bulk Au is characterized by a large (≈ 30%) orbital contribution. This orbital component was retained even when Au atoms formed nanoparticles, playing an important role in stabilizing the spontaneous spin polarization in the Au nanoparticles.     

Quality and loudness judgments for music subjected to compression limiting

Dynamic-range compression (DRC) is used in the music industry to maximize loudness. The amount of compression applied to commercial recordings has increased over time due to a motivating perspective that louder music is always preferred. In contrast to this viewpoint, artists and consumers have argued that using large amounts of DRC negatively affects the quality of music. However, little research evidence has supported the claims of either position. The present study investigated how DRC affects the perceived loudness and sound quality of recorded music. Rock and classical music samples were peak-normalized and then processed using different amounts of DRC. Normal-hearing listeners rated the processed and unprocessed samples on overall loudness, dynamic range, pleasantness, and preference, using a scaled paired-comparison procedure in two conditions: un-equalized, in which the loudness of the music samples varied, and loudness-equalized, in which loudness differences were minimized. Results indicated that a small amount of compression was preferred in the un-equalized condition, but the highest levels of compression were generally detrimental to quality, whether loudness was equalized or varied. These findings are contrary to the "louder is better" mentality in the music industry and suggest that more conservative use of DRC may be preferred for commercial music.     

Big,Strong, Neutral,Twisted, and Chiral π Acids

General synthetic access to expanded π‐acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion–π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron‐withdrawing substituents decreases and the high π acidity needed for strong anion–π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion–π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from ?3.96 to ?4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X‐ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation–π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches ?4.45 eV, whereas two sulfone moieties give a value of ?4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion–π interactions, these conceptually innovative π‐acidic surfaces are also of interest as electron transporters in conductive materials.