Sensitive and selective PET-based diimidazole luminophore for Zn(II) ions: a structure-activity correlation

3-(3-Ethoxymethyl-1H-imidazol-2-yl)-3-(1-ethoxymethyl-1H-imidazol-2-yl)-3H-benzo[de]isochromen-1-one, 4, is a novel photoinduced electron transfer (PET) chemosensor that becomes fluorescent upon binding metal ions and shows a strong preference toward Zn(II) ions. The new bisimidazol PET sensor and its zinc complex were prepared and characterized in terms of their crystal structures, absorption and emission spectra, and orbital energy diagrams. Free 4 is a weakly luminescent species. On the basis of detailed DFT calculations, we suggest that the poor luminescence yield of free 4 originates from its orbital structure in which two pi-orbitals of the two imidazole rings, HOMO and HOMO-1, are situated between two pi-orbitals of the isochromene-one system, HOMO-2 and LUMO. The absorption and emission processes occur between the two pi-orbitals of the isochromene-one system, HOMO-2 and LUMO, and the two pi-imidazole orbitals serve as quenchers for the excited state of the molecule through nonradiative processes. Upon binding Zn(II) ions, 4 becomes a highly luminescent species having a luminescence maximum peaking at 375 nm (lambda(ex) = 329 nm). The significant 900-fold enhancement in luminescence upon binding of the Zn(II) ions is attributed to the stabilization of the pi-orbitals of the imidazole rings upon their engagement in new bonds with the zinc ion. The affinity of 4 to zinc ions in acetonitrile is found to be very high, Ka > 3 x 10(6) M(-1), while with other metals ions, the association constants are considerably weaker.     

Palladium‐Mediated Direct Disulfide Bond Formation in Proteins Containing S‐Acetamidomethyl‐cysteine under Aqueous Conditions

One of the applied synthetic strategies for correct disulfide bond formation relies on the use of orthogonal Cys protecting groups. This approach requires purification before and after the deprotection steps, which prolongs the entire synthetic process and lowers the yield of the reaction. A major challenge in using this approach is to be able to apply one‐pot synthesis under mild conditions and aqueous media. In this study, we report the development of an approach for rapid disulfide bond formation by employing palladium chemistry and S‐acetamidomethyl‐cysteine [Cys(Acm)]. Oxidation of Cys(Acm) to the corresponding disulfide bond is achieved within minutes in a one‐pot operation by applying palladium and diethyldithiocarbamate. The utility of this reaction was demonstrated by the synthesis of the peptide oxytocin and the first total chemical synthesis of the protein thioredoxin‐1. Our investigation revealed a critical role of the Acm protecting group in the disulfide bond formation, apparently due to the generation of a disulfiram in the reaction pathway, which significantly assists the oxidation step.     

Generalized rational approximation in interpolating subspaces of Lp(μ)

We extend the geometric approach of Cheney and Loeb in [2] to the problem of approximation in L_p(μ) by “admissable” generalized rational functions. We obtain a characterization for locally best approximations and find the interpolating condition sufficient for their local unicity. Our results are comparable to those for the linear approximation problem as investigated by Singer and Ault, Deutsch, Morris, and Olson.     

Production of energetic electrons during magnetic reconnection

The production of energetic electrons during magnetic reconnection is explored with full particle simulations and analytic analysis. Density cavities generated along separatrices bounding growing magnetic islands support parallel electric fields that act as plasma accelerators. Electrons because of their low mass are fast enough to make multiple passes through these acceleration cavities and are therefore capable of reaching relativistic energies.     

A second-order approximation to natural convection for large Rayleigh numbers and small Prandtl numbers

The problem under investigation is that of fluid flow within an enclosed rectangular cavity. It is assumed that one wall is maintained at a constant temperature T₁ (hot wall) and the other wall is maintained at a constant temperature T₀ (cold wall). At the remaining walls, two separate cases are studied. In the first, an adiabatic boundary condition is assumed. That is, the normal derivative of the temperature function is assumed to be 0. In the second, it is assumed the temperature varies linearly from T₀ to T₁. The purpose of this paper is the application of a second order numerical technique to the problem of fluid flow within a heated closed cavity. The method is a modification of a method developed by Shay¹ and applied to the driven cavity problem. In order to test the viability of this technique, it was decided to extend the technique to the problem of natural convection in a square. Jones² proposed that this problem is suitable for testing techniques that may be applied to a wide range of practical problems such as reactor insulation, cooling of radioactive waste containers, solar energy collection and others.³ The technique makes use of second-order finite difference approximations to all derivatives in the governing equations. Furthermore, second-order approximations are also used to determine boundary vorticities and, when the adiabatic boundary condition is used, for the boundary temperatures as well. In some works, where second-order approximations are used at interior points, second-order boundary approximations have been sacrificed in favour of a more stable, but first-order boundary approximation. The current approximations are generated by writing the unknown value of a function at a given interior node as a linear combination of unknown function values at all of the neighbouring nodes. Then the function values at these neighbouring nodes are expanded in a Taylor series about the given node. Through appropriate regrouping of terms and the use of the equations to the solved, constraints are imposed on the coefficients of the linear combination to yield a second-order approximation. As it turns out, there are more unknowns than constraints and, as a result, we are left with some freedom in choosing coefficients. In this work this freedom was used to choose coefficients in such a way as to maximize stability of the resulting system of equations. In other words, the approximations to the governing partial differential equation are individually determined at each point dependent on the direction of flow in order to generate the best possible stability. This idea is analogous to that used in the derivation of the upwind method. However, the current method is second-order accurate where the upwind method is only first-order accurate. Thus, what is generated is an easily implemented second-order method that yields a system of equations that has proved easy to solve. The system of equations is solved via the method of successive overrelaxation. The stability of the method is shown in the convergence for a wide range of Rayleigh numbers, Prandtl numbers and mesh sizes. Level curves of the stream, vorticity and temperature functions are provided for Rayleigh numbers (Ra) as large as 100,000, Prandtl numbers (Pr) as small as 0.0001, and mesh sizes as small as 0.0125. Values of the Nusselt number have also been calculated through the use of Simpson's rule, and a second order approximation to the normal derivative of the temperature along the cold wall. Comparisons are made with other current works to aid in the verification of this methods' accuracy and also with the first-order upwind method to demonstrate superiority over the first-order method.     

Ion-molecule reactions and collision-activated dissociation of C4H 4 +. isomers: A case study in the use of the MS3 capabilities of a pentaquadrupole mass spectrometer

Isomeric C₄H ₄ ^+. radical cations vinylacetylene (a), butatriene (b), methylene cyclopropene (c), and the nonaromatic cyclobutadiene (d), generated, respectively, from the neutral precursors 3-butyn-1-ol (1), 1,4-dichloro-2-butyne (2), benzene (3), and 7,8-benzotricyclo [4.2.2.0^2,5]deca-3,7,9-triene (4), undergo diagnostically different ion-molecule reactions with allene, isoprene, furan, and thiophene. It is speculated that adducts are generated by [2 + 2] cycloadditions with the first reagent and [4 + 2] Dials-Alder cycloadditions with isoprene, furan, and thiophene. The initially formed cycloaddition adducts fragment rapidly, isomerize, or undergo further addition of neutral reagent to yield a complex set of products. With a pentaquadrupole mass spectrometer, MS³ experiments that employ three stages of ion mass analysis are used to help elucidate the ion-molecule reactions and to distinguish the isomeric C⁴H ₄ ^+. ions. Among these experiments, the reaction intermediate spectrum reveals the nature of the intermediates connecting the reactant to a selected product while the sequential product spectrum provides mechanistic and structural information on the adducts and other ion-molecule products. The unique combination of ion-molecule reactions with collision-activated dissociation employed here provides valuable information on the chemistry of ionized cyclobutadiene, including its proclivity to undergo [2 + 2] and [4 + 2] cyc1oadditions.     

An extraction-based assay for neutral anionophores: the measurement of high binding constants to steroidal receptors in a nonpolar solvent

The extraction-based protocol for measuring binding constants, developed by Cram and co-workers, has been extended for use with anionic substrates. The method is especially useful for high-affinity receptors, allowing very high binding constants to be measured in nonpolar solvents. Distribution constants K(d) between chloroform and water have been obtained for tetraethylammonium chloride and bromide, thus calibrating the method for these two substrates. Application to steroidal podands 5-9 has confirmed the ability of electron-withdrawing groups to enhance hydrogen-bond donor capabilities. Binding constants of approximately 3 x 10(7) M(-1) have been measured for the most powerful receptor 7. An X-ray crystal structure of 15, the methyl ester analogue of 7, reveals a well-defined binding site preorganised for anion recognition.     

Evidence for an elongated (>60 ion skin depths) electron diffusion region during fast magnetic reconnection

Observations of an extremely elongated electron diffusion region occurring during fast reconnection are presented. Cluster spacecraft in situ observations of an expanding reconnection exhaust reveal a broad current layer ( approximately 10 ion skin depths thick) supporting the reversal of the reconnecting magnetic field together with an intense current embedded at the center that is due to a super-Alfvénic electron outflow jet with transverse scale of approximately 9 electron skin depths. The electron jet extends at least 60 ion skin depths downstream from the X-line.