Binding corrections for reactions on the deuteron in the 3-3 resonance region

Binding corrections evaluated to all orders in a phenomenological nucleon-nucleon potential are compared with the leading term and with a double scattering correction in the Watson expansion for breakup and for coherent reactions on the deuteron at intermediate pion or photon energies. As principal result, we establish that for charged pion photoproduction, and for certain pion induced “spectator” reactions, the binding correction remains sufficiently small that truncation of the Watson expansion at terms of second order in the projectile-nucleon amplitudes is justifiable, but sufficiently large that it cannot be neglected in comparison with multiple scattering corrections. For the reactions π⁺d → π⁺p + spectator neutron and π^?d → π^?n + spectator proton, our theory predicts deviations from the simplest impulse approximation which become very large in well-defined kinematical regions, and should be easily accessible to experimental investigation.     

Protein dynamics revealed in the excitonic spectra of single LH2 complexes

The fluorescence emission spectrum of single peripheral light-harvesting (LH2) complexes of the photosynthetic purple bacterium Rhodopseudomonas acidophila exhibits remarkable dynamics on a time scale of several minutes. Often the spectral properties are quasi-stable; sometimes large spectral jumps to the blue or to the red are observed. To explain the dynamics, every pigment is proposed to be in two conformational substates with different excitation energies, which originate from the conformational state of the protein as a result of pigment-protein interaction. Due to the excitonic coupling in the ring of 18 pigments, the two-state assumption generates a substantial amount of distinct spectroscopic states, which reflect part of the inhomogeneous distributed spectral properties of LH2. To describe the observed dynamics, spontaneous and light-induced transitions are introduced between the two states. For each ‘realization of the disorder’, the spectral properties are calculated using a disordered exciton model combined with the modified Redfield theory to obtain realistic spectral line shapes. The single-molecule fluorescence peak (FLP) distribution, the distribution dependence on the excitation intensity, and the FLP time traces are well described within the framework of this model.     

A Zn(II) ion selective fluorescence sensor that is not affected by Cd(II)

Comparison of sensors sodium-2,6-diamino-(N,N,N′,N′-tetraacetate)-4-methylanisole 1 and sodium-2,6-diamino-(N,N,N′-triacetate)-4-methylanisole 2 reveal that the loss of an acetyl group in 2 leads to a more selective Zn(II) induced fluorescence enhancement and shows no response to any other metal ions including Cd(II). Structural modifications and AM1 calculations indicate that the sensor uses the three acetyl groups and the 3° amino nitrogen for binding the metal ion. AM1 calculations imply a trigonal bipyramidal coordination for Zn(II) with the solvent molecule occupying one of the axial positions.     

Cavitands with introverted functionality stabilize tetrahedral intermediates

The synthesis and characterization of two deepened cavitand hosts with introverted functionality--functional groups directed into the cavity--is described. Two functions can be introverted, alcohol and aldehyde, and they show the formation of hemiacetals and hemiketals on binding small guests with complementary functional groups. The structures of the bound hemiacetals are determined by 1D and 2D NMR studies. The arrangements of the guests in the cavitands enhance the equilibrium constants of carbonyl additions, K/K(ctrl), between 13- and 10(5)-fold, compared to their counterparts in solution. The stabilization of the addition products is due to the prior complexation of the guests and the organized solvation provided to the tetrahedral intermediates by a network of secondary amides at the cavitand rim.     

A deep cavitand catalyzes the Diels-Alder reaction of bound maleimides

A deep cavitand catalyzes Diels-Alder reactions of bound maleimides via activation of the dienophile by interaction with the organized hydrogen bonding network at the cavitand rim. Rapid in-out exchange of reactant and product allows efficient turnover. The increase in steric bulk of the reaction product lessens its binding affinity, reducing (and in some cases completely eliminating) product inhibition.     

Self-complexed deep cavitands: alkyl chains coil into a nearby cavity

[structure: see text]. A series of self-complexing tetrabenzimidazole cavitands have been synthesized. Alkyl chains appended to the rim helically coil into the cavity in competitive organic solvents. These "flexible arms" exchange with each other, a process shown by 2D NMR to proceed via an intermediate solvent-containing species.     

Bent alkanes in a new thiourea-containing capsule

The synthesis of a cavitand featuring thiourea hydrogen bonding sites and its dimerization in the presence of suitable guests are reported. Dimerization creates a capsule host wider than the corresponding urea or imide structures, and longer alkanes can be accommodated. Specifically, n-C(15)H(32) is encapsulated, but this guest appears folded inside as deduced from NMR studies. Apparently, the plasticity of hydrogen bonds between thiourea groups allows a stable encapsulation complex to persist in solution even though the guest is contorted.     

Theoretical study of hydrogen bonding in homodimers and heterodimers of amide, boronic acid, and carboxylic acid, free and in encapsulation complexes

The homodimers and the heterodimers of two amides, two boronic acids, and two carboxylic acids have been calculated in the gas phase and in N,N-dimethylformamide (DMF) and CCl(4) solvents using the DFT (M06-2X and M06-L) and the MP2 methods in conjunction with the 6-31G(d,p) and 6-311+G(d,p) basis sets. Furthermore, their pairwise coencapsulation was studied to examine its effect on the calculated properties of the hydrogen bonds at the ONIOM[M06-2X/6-31G(d,p);PM6], ONIOM[MP2/6-31G(d,p); PM6], and M06-2X/6-31G(d,p) levels of theory. The present work is directed toward the theoretical rationalization and interpretation of recent experimental results on hydrogen bonding in encaptulation complexes [D. Ajami et al. J. Am. Chem. Soc. 2011, 133, 9689-9691]. The calculated dimerization energy (ΔE) values range from 0.74 to 0.35 eV for the different dimers in the gas phase, with the ordering carboxylic homodimers > amide-carboxylic dimers > amide homodimers > boronic-carboxylic dimers > amide-boronic dimers > boronic homodimers. In solvents, generally smaller ΔE values are calculated with only small variations in the ordering. In the capsule, the ΔE values range between 0.67 and 0.33 eV with practically the same ordering as in the gas phase. The calculated % distributions of the encapsulated dimers, taking into account statistical factors, are in agreement with the experimental distribution, where the occurrence of boronic homodimer dominates, even though it is calculated to have the smallest ΔE.     

Cordioxime: a new dioxime gamma-lactam from Cordia platythyrsa

Cordia platythyrsa Baker is known for its medicinal value. This paper deals with a phytochemical investigation of this species, from which cordioxime (1), a new dioxime y-lactam has been isolated. Its structure was determined by comprehensive analyses of its 1H and 13C NMR, COSY, HMQC, and HMBC spectroscopic, and HREIMS data. The remaining two known compounds were identified as beta-sitosterol, and beta-sitosterol glucopyranoside.