Photoinduced electron transfer in a triad that can be assembled/disassembled by two different external inputs. Toward molecular-level electrical extension cables

We have designed, synthesized, and investigated a self-assembling supramolecular system which mimics, at a molecular level, the function performed by a macroscopic electrical extension cable. The system is made up of three components, 12+, 2-H3+, and 3. Component 12+ consists of two moieties: a [Ru(bpy)3]2+ unit, which plays the role of an electron donor under light excitation, and a DB24C8 crown ether, which fulfills the function of a socket. The wire-type component 2-H3+ is also composed of two moieties, a secondary dialkylammonium-ion center and a bipyridinium unit, which thread into the DB24C8 crown-ether socket of 12+ and the 1/5DN38C10 crown-ether socket 3, respectively. The photochemical, photophysical, and electrochemical properties of the three separated components, of the 12+ superset 2-H3+ and 2-H3+ subset 3 dyads, and of the 12+ superset 2-H3+ subset 3 triad have been investigated in CH2Cl2 solution containing 2% MeCN. Reversible connection/disconnection of the two plug/socket systems can be controlled independently by acid/base and redox stimulation. The behavior of the various different dyads and triad has been monitored by light absorption and emission spectroscopies, as well as by electrochemical techniques. In the fully connected 12+ superset 2-H3+ subset 3 triad, light excitation of the [Ru(bpy)3]2+ unit of component 12+ is followed by electron transfer (k = 2.8 x 108 s-1) to the bipyridinium unit of component 2-H3+, which is plugged into component 3. Possible schemes to obtain improved molecular-level electrical extension cables are discussed.     

A Basis for the Top Homology of a Generalized Partition Lattice

For a fixed positive integer k, consider the collection of all affine hyperplanes in n-space given by xi – xj = m, where i, j [n], i j, and m {0, 1,..., k}. Let Ln,k be the set of all nonempty affine subspaces (including the empty space) which can be obtained by intersecting some subset of these affine hyperplanes. Now give Ln,k a lattice structure by ordering its elements by reverse inclusion. The symmetric group Gn acts naturally on Ln,k by permuting the coordinates of the space, and this action extends to an action on the top homology of Ln,k. It is easy to show by computing the character of this action that the top homology is isomorphic as an Gn-module to a direct sum of copies of the regular representation, CGn. In this paper, we construct an explicit basis for the top homology of Ln,k, where the basis elements are indexed by all labelled, rooted, (k + 1)-ary trees on n-vertices in which the root has no 0-child. This construction gives an explicit Gn-equivariant isomorphism between the top homology of Ln,k and a direct sum of copies of CGn.     

Some charge transfer reactions of excited aromatic compounds with sulphides

Photo-reductive dehalogenation of aromatic halides to their parent hydrocarbons is stimulated in the presence of electron donors such as di-ethyl sulphide. Evidence is presented for the involvement of radicals ions in these reactions.     

Discovery of structurally diverse natural product antagonists of chemokine receptor CXCR3

The chemokines (CXCL9, CXCL10 and CXCL11) and associated CXCR3 receptor are expressed during the inflammatory process from multiple sclerosis, atherosclerosis or organ transplantation resulting in the recruitment of lymphocytes leading to tissue damage. It is hypothesized that blocking of the ligand/CXCR3 receptor interaction has potential to provide opportunity for development of agents that would block tissue rejection. In this paper, four classes of natural product inhibitors (IC₅₀ ranging 0.1–41 M) have been described that block the CXCR3 receptor interaction of IP-10 ligand. These include a cyclic thiopeptide (duramycin), polyketide glycosides (roselipins), steroidal glycosides (hypoglausin A and dioscin) and a novel alkyl pyridinium alkaloid that were isolated by bioassay-guided fractionation of the organic extracts derived from actinomycete, fungal, plant and marine sources and discovered using ¹²⁵ I IP-10/CXCR3 binding assay. Duramycin was the most potent with an IC₅₀ of 0.1 M. Roselipins 2A, 2B and 1A showed IC₅₀ values of 14.6, 23.5, and 41 M, respectively. Diosgenin glycosides dioscin, hypoglaucin A and kallstroemin D exhibited IC₅₀ values of 2.1, 0.47 and 3 M, respectively. A novel cyclic 3-alkyl pyridinium salt isolated from a sponge displayed a binding IC₅₀ of 0.67 M.     

Unprecedented (Cu2Ln)n complexes (Ln = Gd3+, Tb3+): a new "single chain magnet"

The magnetic study of a trinuclear Cu-Gd-Cu complex confirms that such basic units self-assemble to yield a high spin species. A nice fit of the magnetic data is obtained for an infinite chain of tetranuclear Gd(2)Cu(2) motifs linked through the Gd ions located at the opposite vertexes of the tetranuclear motifs according to two Cu-Gd coordination modes, a double bridging through phenoxo and alkoxo oxygen atoms and a single bridging through deprotonated amide functions. The two interaction pathways are ferromagnetic. Alternating current susceptibility measurements confirm that the equivalent copper-terbium entity is a single chain magnet with a barrier height for reversal of the magnetization equal to 28.5 K.     

The effect of recording and analysis bandwidth on acoustic identification of delphinid species

Because many cetacean species produce characteristic calls that propagate well under water, acoustic techniques can be used to detect and identify them. The ability to identify cetaceans to species using acoustic methods varies and may be affected by recording and analysis bandwidth. To examine the effect of bandwidth on species identification, whistles were recorded from four delphinid species (Delphinus delphis, Stenella attenuata, S. coeruleoalba, and S. longirostris) in the eastern tropical Pacific ocean. Four spectrograms, each with a different upper frequency limit (20, 24, 30, and 40 kHz), were created for each whistle (n = 484). Eight variables (beginning, ending, minimum, and maximum frequency; duration; number of inflection points; number of steps; and presence/absence of harmonics) were measured from the fundamental frequency of each whistle. The whistle repertoires of all four species contained fundamental frequencies extending above 20 kHz. Overall correct classification using discriminant function analysis ranged from 30% for the 20-kHz upper frequency limit data to 37% for the 40-kHz upper frequency limit data. For the four species included in this study, an upper bandwidth limit of at least 24 kHz is required for an accurate representation of fundamental whistle contours.     

Multiplex inhibitor screening and kinetic constant determinations for yeast hexokinase using mass spectrometry based assays

An electrospray ionization mass spectrometry based assay was developed for kinetic measurements and inhibitor screening of yeast hexokinase. There is considerable discrepancy in the literature as to the accuracy of kinetic data obtained for hexokinase. In the assay described herein, the product, glucose 6-phosphate was directly monitored by ion trap mass spectrometry and quantified using an internal standard, 2 deoxy-glucose 6-phosphate. The kinetic parameters, K(M) and V(max) for the two substrates were determined without using a coupling enzyme as is normally employed in the traditional spectrophotometric assay for systems lacking a chromophore. In addition, hexokinase was successfully immobilized onto an amino-link gel, and a mock library was screened against the immobilized enzyme for the identification of possible inhibitors. After comparing the mass spectra of the library before and after incubation, trehalose 6-phosphate, ADP, and oxidized glutathione were differentiated from other weak or non-inhibitors. Inhibition behavior of ADP with respect to ATP was further evaluated with the ESI-MS assay and the value of K(i) was determined. This ESI-MS assay was demonstrated to be both accurate and precise for determining kinetic constants and for identifying enzyme inhibitors.