Short-chain reactive probes as tools to unravel the Pseudomonas aeruginosa quorum sensing regulon

In recent years, the world has seen a troubling increase in antibiotic resistance among bacterial pathogens. In order to provide alternative strategies to combat bacterial infections, it is crucial deepen our understanding into the mechanisms that pathogens use to thrive in complex environments. Most bacteria use sophisticated chemical communication systems to sense their population density and coordinate gene expression in a collective manner, a process that is termed “quorum sensing” (QS). The human pathogen Pseudomonas aeruginosa uses several small molecules to regulate QS, and one of them is N-butyryl-l-homoserine lactone (C₄-HSL). Using an activity-based protein profiling (ABPP) strategy, we designed biomimetic probes with a photoreactive group and a ‘click’ tag as an analytical handle. Using these probes, we have identified previously uncharacterized proteins that are part of the P. aeruginosa QS network, and we uncovered an additional role for this natural autoinducer in the virulence regulon of P. aeruginosa, through its interaction with PhzB1/2 that results in inhibition of pyocyanin production.

Short-chain reactive probes can be used as tools to shed new light on virulence mechanisms in bacterial pathogens.     

The study of degradable polystyrene: Photolysis in solution and photo-oxidation in films

Radical copolymerization of styrene with benzalacetophenone or benzalacetone in bulk or in suspension yielded copolymers with as much as 10 wt% of carbonyl monomer. They were characterized by GPC, viscometry and spectroscopy. Photolysis of copolymers was investigated in benzene at 313 nm. Quantum yields for main chain scissions were about 0.005 and the life-time of the triplet state was 5 nsec. Photo-oxidation in films was followed by monitoring the decrease in molecular weight and by i.r. and emission spectra. Quantum yield for main chain scission in films was about 0.0002. During photooxidation in film, the molecular weight distribution widened. A new i.r.-band appeared at 3580 cm^?1 and the carbonyl band was spread between 1700 and 1800 cm^?1. In the emission spectra, the vibrational resolved emission (typical of the carbonyl chromophore) disappeared.     

Synthesis and Properties of First Bis(fluoreno)crownophanes

Alkylation of 2,7-dihydroxy-9H-fluoren-9-one with 2-(2-chloroethoxy)ethanol, 2-[2-(2-chloroethoxy)-ethoxy]ethanol, and 2-{2-[2-(2-chloroethoxy)ethoxy]ethoxy}ethanol in dimethylformamide in the presence of potassium carbonate gave 78–80% of the corresponding diols which were treated with p-toluenesulfonyl chloride in a dioxanechloroform mixture in the presence of triethylamine at 0– 5°C (30 h). The resulting bis(p-toluene-sulfonates) were brought into condensation with 2,7-dihydroxy-9H-fluoren-9-one in a very dilute solution in dimethylformamide containing anhydrous potassium carbonate at 80–85°C. Appropriate treatment of the reaction mixture, followed by chromatographic purification afforded 53–27% of the first representatives of a new class of cyclophanes, bis(oxofluoreno)crownophanes. Raising the temperature to 95–105°C resulted in an appreciable decrease of the product yield. The yield of the target products did not increase on replacement of potassium carbonate by cesium carbonate.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 144–149.Original Russian Text Copyright © 2005 by Lyapunov, Kirichenko, Kulygina, Luk’yanenko.     

Transitions between disordered phases in supercooled liquid silicon

We have investigated the transitions between disordered phases in supercooled liquid silicon using computer simulations. The thermodynamic properties were directly obtained from the free energy, which was computed using the recently proposed reversible scaling method. The calculated free energies of the crystalline and liquid phases of silicon at zero pressure, obtained using the environment dependent interatomic potential, are in excellent agreement with the available experimental data. The results show that, at zero pressure, a weak first-order liquid-liquid transition occurs at 1135 K and a continuous liquid-amorphous transition takes place at 843 K. These results are consistent with the existence of a second critical point for the liquid-liquid transition at a negative pressure.     

Kobalt(III)ammin-derivate einiger Reineckesalz-Analoga mit Xylidinen

Zusammenfassung Es wurden 34 neue Komplexsalze durch doppelte Umsetzung aus wäßr.-alkohol. Lösungen der folgenden Reineckeat-Analoga: [Cr(NCS)₄(m-xylidin)₂]^–, [Cr(NCS)₄(p-xyl)₂]^– und Hexammin-, Monoacido-pentammin- und Diacido-tetramminkobalt(III)-komplexsalze erhalten. Es wurden in einigen Fällen Unterschiede in physiko-chemischen Eigenschaften, wie Farbtönung, Kristallform, Löslichkeit und papierchromatographischeR _f-Werte, bei den stellungsisomeren Salzen vom Typus: Kation · [Cr(NCS)₄(xyl)₂] und auch bei den Koordinationsisomerpaaren: [Co(DH)₂(m-xyl)₂] [Cr(NCS)₄(p-xyl)₂] und [Co(DH)₂(p-xyl)₂] [Cr(NCS)₄(m-xyl)₂] usw. beobachtet.

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Cobalt(III)ammine derivatives of some reineckate analogues with xylidines

34 new complex salts were prepared by double conversion of the reineckate analogues [Cr(NCS)₄(m-xylidine)₂]^–, [Cr(NCS)₄(p-xyl)₂]^–, with the hexammine-, monoacido-pentammine- and diacidotetrammine-complexes of Co(III). In some of the position and coordination isomeres differences of the standard physico-chemical properties, i.e. color, crystal form, solubility and paper chromatographyR _f-values were observed.

     

Bispectral KP solutions and linearization of Calogero-Moser particle systems

Rational and soliton solutions of the KP hierarchy in the subgrassmannianGr ₁ are studied within the context of finite dimensional dual grassmannians. In the rational case, properties of the tau function, , which are equivalent to bispectrality of the associated wave function, , are identified. In particular, it is shown that there exists a bound on the degree of all time, variables in if and only if is a rank one bispectral wave function. The action of the bispectral involution, , in the generic rational case is determined explicitly in terms of dual grassmannian parameters. Using the correspondence between rational solutions, and particle systems, it is demonstrated that is a linearizing map of the Calogero-Moser particle system and is essentially the map introduced by Airault, McKean and Moser in 1977 [2].Research supported by NSA Grant MDA904-92-H-3032     

Analysis of cement and cement raw meal by atomic absorption spectrophotometry using a new fusion agent

A new fusion agent is proposed for the analysis of cement and cement raw meal using AAS. In the described method, 0.8 g of the fusion agent, consisting of equal portions of oxalic acid, lithium carbonate and lithium tetraborate, was mixed with 0.2 g of the sample, and the mixture was fused for 10 min at 925 degrees C in a platinum crucilbe. The fusion cake was dissolved with dilute hydrochloric acid (1 + 10) and diluted to 500 ml for the determination of Si, Al, Fe, Ti, Na and K expressed as SiO(2), Al(2)O(3), Fe(2)O(3), TiO(2), Na(2)O, and K(2)O respectively. For the determination of Ca and Mg (expressed as CaO and MgO respectively), 10 ml of the previous sample solution were mixed with 4 ml of 6% (m/v) lanthanum nitrate solution and the solution was diluted to 100 ml. The method was found to have good accuracy and precision. The time required to determine the eight elements was around 80 min for each sample.     

Inclusion-exclusion: Exact and approximate

It is often required to find the probability of the union of givenn eventsA ₁ ,...,A _n . The answer is provided, of course, by the inclusion-exclusion formula: Pr(A _i )= _i – _i<j Pr(A _i A _j )±.... Unfortunately, this formula has exponentially many terms, and only rarely does one manage to carry out the exact calculation. From a computational point of view, finding the probability of the union is an intractable, #P-hard problem, even in very restricted cases. This state of affairs makes it reasonable to seek approximate solutions that are computationally feasible. Attempts to find such approximate solutions have a long history starting already with Boole [1]. A recent step in this direction was taken by Linial and Nisan [4] who sought approximations to the probability of the union, given the probabilities of allj-wise intersections of the events forj=1,...k. The developed a method to approximate Pr(A _i ), from the above data with an additive error of exp . In the present article we develop an expression that can be computed in polynomial time, that, given the sums _|S|=j Pr( _iS A _i ) forj=1,...k, approximates Pr(A _i ) with an additive error of exp . This error is optimal, up to the logarithmic factor implicit in the notation.The problem of enumerating satisfying assignments of a boolean formula in DNF formF=v _l ^m C _i is an instance of the general problem that had been extensively studied [7]. HereA _i is the set of assignments that satisfyC _i , and Pr( _iS A _i )=a _S /2ⁿ where _iS C _i is satisfied bya _S assignments. Judging from the general results, it is hard to expect a decent approximation ofF's number of satisfying assignments, without knowledge of the numbersa _S for, say, all cardinalities . Quite surprisingly, already the numbersa _S over |S|log(n+1)uniquely determine the number of satisfying assignments for F.We point out a connection between our work and the edge-reconstruction conjecture. Finally we discuss other special instances of the problem, e.g., computing permanents of 0,1 matrices, evaluating chromatic polynomials of graphs and for families of events whose VC dimension is bounded.Work supported in part by a grant of the Binational Israel-US Science Foundation.Work supported in part by a grant of the Binational Israel-US Science Foundation and by the Israel Science Foundation.     

Charge separation versus recombination in dye-sensitized nanocrystalline solar cells: the minimization of kinetic redundancy

In this paper we focus upon the electron injection dynamics in complete dye-sensitized nanocrystalline metal oxide solar cells (DSSCs). Electron injection dynamics are studied by transient absorption and emission studies of DSSCs and correlated with device photovoltaic performance and charge recombination dynamics. We find that the electron injection dynamics are dependent upon the composition of the redox electrolyte employed in the device. In a device with an electrolyte composition yielding optimum photovoltaic device efficiency, electron injection kinetics exhibit a half time of 150 ps. This half time is 20 times slower than that for control dye-sensitized films covered in inert organic liquids. This retardation is shown to result from the influence of the electrolyte upon the conduction band energetics of the TiO2 electrode. We conclude that optimum DSSC device performance is obtained when the charge separation kinetics are just fast enough to compete successfully with the dye excited-state decay. These conditions allow a high injection yield while minimizing interfacial charge recombination losses, thereby minimizing "kinetic redundancy" in the device. We show furthermore that the nonexponential nature of the injection dynamics can be simulated by a simple inhomogeneous disorder model and discuss the relevance of our findings to the optimization of both dye-sensitized and polymer based photovoltaic devices.     

High-performance liquid radiochromatography: Its application for stability study of [3H] stobadin

An HPLC method was developed for studying the stability of [³H] stobadin stored in physiological saline or buffers at various pH. Optimum conditions for the separation of degradation products were elaborated. A high-performance liquid chromatograph equipped with a radioactivity detector was used.