The practical synthesis of a novel and highly potent analogue of bryostatin

Macrocycle 1 is a new highly potent analogue of bryostatin 1, a promising anti-cancer agent currently in human clinical trials. In vitro, 1 displays picomolar affinity for PKC and exhibits over 100-fold greater potency than bryostatin 1 when tested against various human cancer cell lines. Macrocycle 1 can be generated in clinically required amounts by chemical synthesis in only 19 steps (LLS) and represents a new clinical lead for the treatment of cancer.     

Phase and orientational ordering of low molecular weight rod molecules in a quenched liquid crystalline polymer matrix with mobile side chains

We study the phase diagram and orientational ordering of guest liquid crystalline (LC) rods immersed in a quenched host made of a liquid crystalline polymer (LCP) matrix with mobile side chains. The LCP matrix lies below the glass transition of the polymer backbone. The side chains are mobile and can align to the guest rod molecules in a plane normal to the local LCP chain contour. A field theoretic formulation for this system is proposed and the effects of the LCP matrix on LC ordering are determined numerically. We obtain simple analytical equations for the nematic/isotropic phase diagram boundaries. Our calculation show a nematic-nematic (N/N) first order transition from a guest stabilized to a guest-host stabilized region and the possibility of a reentrant transition from a guest stabilized nematic region to a host only stabilized regime separated by an isotropic phase. A detailed study of thermodynamic variables and interactions on orientational ordering and phases is carried out and the relevance of our predictions to experiments and computer simulations is presented.     

Altered mechanisms of reactions of phosphate esters bridging a dinuclear metal center

Kinetic isotope effects in the nucleophile and leaving group were obtained for the reaction of p-nitrophenyl phosphate monoester coordinated to a dinuclear Co(III) complex. The metal complex of the p-nitrophenyl phosphate monoester was found to hydrolyze by a single-step concerted mechanism, with significant nucleophilic participation in the transition state. By contrast, the hydrolysis of uncomplexed p-nitrophenyl phosphate occurs by a very loose transition state with little bond formation to the nucleophile. Previously, the metal complex of the diester methyl-p-nitrophenyl phosphate was found to hydrolyze via a two-step addition-elimination mechanism, in contrast to the concerted hydrolysis mechanism followed by uncomplexed diesters with the p-nitrophenolate leaving group. These results show that coordination to a metal complex can significantly alter the mechanism of phosphoryl transfer.     

Current mass spectrometry strategies for selenium speciation in dietary sources of high-selenium

This document reviews the most relevant mass spectrometry approaches to selenium (Se) speciation in high-Se food supplements in terms of qualitative and quantitative Se speciation and Se-containing species identification, with special reference to high-Se yeast, garlic, onions and Brazil nuts. Important topics such as complexity of Se speciation in these materials and the importance of combining Se-specific detection and molecule-specific determination of the particular species of this element in parallel with chromatography, to understand their nutritional role and cancer preventive properties are critically discussed throughout. The versatility and potential of mass spectrometric detection in this field are clearly demonstrated. Although great advances have been achieved, further developments are required, especially if speciatedcertified reference materials (CRMs) are to be produced for validation of measurements of target Se-containing species in Se-food supplements.     

Development and validation of a glass-silicon microdroplet-based system to measure sulfite concentrations in beverages

Sulfite is often added to beverages as an antioxidant and antimicrobial agent. In fermented beverages, sulfite is also naturally produced by yeast cells. However, sulfite causes adverse health effects in asthmatic patients and accurate measurement of the sulfite concentration is therefore very important. Current sulfite analysis methods are time- and reagent-consuming and often require costly equipment. Here, we present a system allowing sensitive, ultralow-volume sulfite measurements based on a reusable glass-silicon microdroplet platform on which microdroplet generation, addition of enzymes through chemical-induced emulsion destabilization and pillar-induced droplet merging, emulsion restabilization, droplet incubation, and fluorescence measurements are integrated. In a first step, we developed and verified a fluorescence-based enzymatic assay for sulfite by measuring its analytical performance (LOD, LOQ, the dynamic working range, and the influence of salts, colorant, and sugars) and comparing fluorescent microplate readouts of fermentation samples with standard colorimetric measurements using the 5,5′-dithiobis-(2-nitrobenzoic acid) assay of the standard Gallery Plus Beermaster analysis platform. Next, samples were analyzed on the microdroplet platform, which also showed good correlation with the standard colorimetric analysis. Although the presented platform does not allow stable reinjection of droplets due to the presence of a tight array of micropillars at the fluidics entrances to prevent channel clogging by dust, removing the pillars, and integrating miniaturized pumps and optics in a future design would allow to use this platform for high-throughput, automated, and portable screening of microbes, plant, or mammalian cells.

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A new thermoelectric material: CsBi4Te6

The highly anisotropic material CsBi(4)Te(6) was prepared by the reaction of Cs/Bi(2)Te(3) around 600 degrees C. The compound crystallizes in the monoclinic space group C2/m with a = 51.9205(8) A, b = 4.4025(1) A, c = 14.5118(3) A, beta = 101.480(1) degrees, V = 3250.75(11) A(3), and Z = 8. The final R values are R(1) = 0.0585 and wR(2) = 0.1127 for all data. The compound has a 2-D structure composed of NaCl-type [Bi(4)Te(6)] anionic layers and Cs(+) ions residing between the layers. The [Bi(4)Te(6)] layers are interconnected by Bi-Bi bonds at a distance of 3.2383(10) A. This material is a narrow gap semiconductor. Optimization studies on the thermoelectric properties with a variety of doping agents show that the electrical properties of CsBi(4)Te(6) can be tuned to yield an optimized thermoelectric material which is promising for low-temperature applications. SbI(3) doping resulted in p-type behavior and a maximum power factor of 51.5 microW/cm.K(2) at 184 K and the corresponding ZT of 0.82 at 225 K. The highest power factor of 59.8 microW/cm.K(2) at 151 K was obtained from 0.06% Sb-doped material. We report here the synthesis, physicochemical properties, doping characteristics, charge-transport properties, and thermal conductivity. Also presented are studies on n-type CsBi(4)Te(6) and comparisons to those of p-type.     

Preparation and dilute solution properties of model gemini nonionic surfactants

Dimeric poly(ethylene oxide) surfactants (or nonionic gemini surfactants) with the structure (Cn-2H2n-3CHCH2O(CH2CH2O)mH)2(CH2)6 (or GemnEm), where n is the alkyl length and m is the average number of ethylene oxides per head group, were synthesized. Surfactants were synthesized with alkyl chain lengths n = 12, 14, and 20 and m = 5, 10, 15, 20, and 30. Water solubilities and cloud temperatures at 1 wt% were determined by measuring turbidity as a function of temperature. Cloud temperatures increase with m and decrease with n, as observed for conventional surfactants. For large m the cloud temperatures were all above 100 degrees C. Surfactants with small m (i.e., n = 12, 14, m = 5 and n = 20, m = 10) were insoluble at room temperature, forming two-phase mixtures. Critical micelle concentrations (CMCs) were measured using a pyrene fluorescence method and are all in the range of 10(-7) to 10(-6) M, with the lowest values from the surfactants with large n and small m. CMCs of mixtures with both anionic and nonionic conventional (monomeric) surfactants were well described by an ideal mixing model.     

Sign changes in the prime number theorem

The Ramanujan Journal - Let V(T) denote the number of sign changes in $$\psi (x) - x$$ for $$x\in [1, T]$$ . We show that $$\liminf _{T\rightarrow \infty } V(T)/\log T\ge \gamma _{1}/\pi +...     

Interspike interval embedding of chaotic signals

According to a theorem of Takens [Lecture Notes in Mathematics (Springer-Verlag, Berlin, 1981), Vol. 898], dynamical state information can be reproduced from a time series of amplitude measurements. In this paper we investigate whether the same information can be reproduced from interspike interval (ISI) measurements. Assuming an integrate-and-fire model coupling the dynamical system to the spike train, there is a one-to-one correspondence between the system states and interspike interval vectors of sufficiently large dimension. The correspondence implies in particular that a data series of interspike intervals, formed in this manner, can be forecast from past history. This capability is demonstrated using a nonlinear prediction algorithm, and is found to be robust to noise. A set of interspike intervals measured from a simple neuronal circuit is studied for deterministic structure using a prediction error statistic. (c) 1995 American Institute of Physics.