Direct evidence on the existence of [Mo132]Keplerate-type species in aqueous solution

We demonstrate the existence of discrete single molecular [Mo(132)] Keplerate-type clusters in aqueous solution. Starting from a discrete spherical [Mo(132)] cluster, the formation of an open-basket-type [Mo(116)] defect structure is shown for the first time in solution using analytical ultracentrifugation sedimentation velocity experiments.     

Homolysis of the peroxynitrite anion detected with permanganate

The reaction of peroxynitrite with violet-colored MnO4- leads to the formation of green MnO42-. The rate constant for the reaction at pH 11.7, 5.5 mM ionic strength, and 25 degrees C, 0.020 +/- 0.001 s(-1), is independent of the MnO4- concentration; homolysis of ONOO- to NO* and O2*- is the rate-determining step. Both NO* and O2*- react with MnO4- with rate constants of (3.5 +/- 0.7) x 10(6) M(-1)s(-1) and (5.7 +/- 0.9) x 10(5) M(-1)s(-1), respectively. The activation volume and activation energy for breaking the N-O bond are 12.6 +/- 0.8 cm(3)mol(-1) and 102 +/- 2 kJ mol(-1), respectively. In combination with the known standard Gibbs energies of formation of NO* and O2*-, the rate of the reaction of NO* and O2*-, and the pKa of ONOOH, we find a standard Gibbs energy of formation of ONOO- of +68 +/- 1 kJ mol(-1), and of ONOOH of +31 +/- 1 kJ mol(-1).     

Effect of broadband-noise masking on the behavioral response of a harbor porpoise (Phocoena phocoena) to 1-s duration 6-7 kHz sonar up-sweeps

Naval sonar systems produce signals which may affect the behavior of harbor porpoises, though their effect may be reduced by ambient noise. To show how natural ambient noise influences the effect of sonar sweeps on porpoises, a porpoise in a pool was exposed to 1-s duration up-sweeps, similar in frequency range (6-7 kHz) to those of existing naval sonar systems. The sweep signals had randomly generated sweep intervals of 3-7 s (duty cycle: 19%). Behavioral parameters during exposure to signals were compared to those during baseline periods. The sessions were conducted under five background noise conditions: the local normal ambient noise and four conditions mimicking the spectra for wind-generated noise at Sea States 2-8. In all conditions, the sweeps caused the porpoise to swim further away from the transducer, surface more often, swim faster, and breathe more forcefully than during the baseline periods. However, the higher the background noise level, the smaller the effects of the sweeps on the surfacing behavior of the porpoise. Therefore, the effects of naval sonar systems on harbor porpoises are determined not only by the received level of the signals and the hearing sensitivity of the animals but also by the background noise.     

Kinetics and mechanism of urethane formation catalyzed by organotin compounds. II. The reaction of phenyl isocyanate with methanol in DMF and cyclohexane under the action of dibutyltin diacetate

The kinetics of the dibutyltin diacetate (DBTDA)-catalyzed reaction of phenyl isocyanate with methanol in DMF and cyclohexane have been studied by monitoring the rate of change of the absorbance of the reaction mixture at 281.6 and 280.9 nm, respectively. Our results indicate that the mechanism of the reaction is independent of the nature of the (inert) solvent. The subsequent reaction steps are (i) complexation of methanol to DBTDA, (ii) dissociation of the complex into a proton and an anion of composition [(n-C₄H₉)₂Sn(OCOCH₃)₂(OCH₃)]^?, (iii) insertion of the isocyanate into the tin—alkoxy bond (the rate-determining step), and (iv) methanolysis of the thus-formed urethane precursor with simultaneous regeneration of the anion. The rate of the catalyzed reaction increases on goin from coordinating to noncoordinating solvents. The following sequence in order of increasing rate constant was observed: DMF < dibutyl ether < cyclohexane. This is because in coordinating solvents, DBTDA and methanol, apart from forming a complex with each other, also form complexes with the solvent.     

Redshifted and Near‐infrared Active Analog Pigments Based upon Archaerhodopsin‐3

Archaerhodopsin‐3 (AR3) is a member of the microbial rhodopsin family of hepta‐helical transmembrane proteins, containing a covalently bound molecule of all‐trans retinal as a chromophore. It displays an absorbance band in the visible region of the solar spectrum (λmax 556 nm) and functions as a light‐driven proton pump in the archaeon Halorubrum sodomense. AR3 and its mutants are widely used in neuroscience as optogenetic neural silencers and in particular as fluorescent indicators of transmembrane potential. In this study, we investigated the effect of analogs of the native ligand all‐trans retinal A1 on the spectral properties and proton‐pumping activity of AR3 and its single mutant AR3 (F229S). While, surprisingly, the 3‐methoxyretinal A2 analog did not redshift the absorbance maximum of AR3, the analogs retinal A2 and 3‐methylamino‐16‐nor‐1,2,3,4‐didehydroretinal (MMAR) did generate active redshifted AR3 pigments. The MMAR analog pigments could even be activated by near‐infrared light. Furthermore, the MMAR pigments showed strongly enhanced fluorescence with an emission band in the near‐infrared peaking around 815 nm. We anticipate that the AR3 pigments generated in this study have widespread potential for near‐infrared exploitation as fluorescent voltage‐gated sensors in optogenetics and artificial leafs and as proton pumps in bioenergy‐based applications.     

Metathesis reactions for the synthesis of ring-fused carbazoles

[reactions: see text] The metathesis reaction is used as a key step for the synthesis of the indolo[2,3-a]carbazole core of rebeccamycin 13 and the sulfur analog of furostifoline 21. Using the same methodology for the attempted synthesis of furostifoline, we unexpectedly formed tert-butyl-2a-methyl-1,2,2a,10c-tetrahydro-6H-cyclobuta[c]furo[3,2-a]carbazole-6-carboxylate 26 from the unstable diene, tert-butyl 2-(2-isopropenyl-3-furyl)-3-vinyl-1H-indole-1-carboxylate 25, presumably via a spontaneous pi8 electrocyclization reaction.     

Influence of cationic composition and pH on the formation of metal stearates at oil-water interfaces

We study the formation of layers of metal stearates at the interface between a decane solution of stearic acid and aqueous salt solutions of variable composition and pH by monitoring the evolution of their mechanical, optical, and chemical properties as a function of time after formation of the interface. For values of the pH below the pK(a) of stearic acid hardly any interfacial activity is observed. For pH > pK(a), stearic acid deprotonates at the interface and forms metal stearates, eventually leading to the formation of macroscopic solid layers. Dynamic interfacial tension measurements reveal that the process takes place in several stages, which we attribute to the successive formation of dilute and dense monolayers followed by three-dimensional growth. In the presence of divalent ions, the solid layers display a significant increase in the dilatational storage modulus. Experiments performed with an aqueous phase containing multiple cation species (artificial seawater) give rise to particularly pronounced growth of solid layers, which preferentially incorporate Ca(2+) as revealed by X-ray photoelectron and infrared spectroscopy. Our results highlight in particular the importance of the complex synergistic effects of simultaneously present monovalent and divalent cation species on the interfacial adsorption.     

Classical proof forestry

Classical proof forests are a proof formalism for first-order classical logic based on Herbrand’s Theorem and backtracking games in the style of Coquand. First described by Miller in a cut-free setting as an economical representation of first-order and higher-order classical proof, defining features of the forests are a strict focus on witnessing terms for quantifiers and the absence of inessential structure, or ‘bureaucracy’.This paper presents classical proof forests as a graphical proof formalism and investigates the possibility of composing forests by cut-elimination. Cut-reduction steps take the form of a local rewrite relation that arises from the structure of the forests in a natural way. Yet reductions, which are significantly different from those of the sequent calculus, are combinatorially intricate and do not exclude the possibility of infinite reduction traces, of which an example is given.Cut-elimination, in the form of a weak normalisation theorem, is obtained using a modified version of the rewrite relation inspired by the game-theoretic interpretation of the forests. It is conjectured that the modified reduction relation is, in fact, strongly normalising.