The newly prepared water-soluble naphthalene tweezer 2a and anthracene clip 4a (substituted both with lithium methanephosphonate groups in the central spacer unit) undergo an unexpected self-assembly in aqueous solution. The highly ordered intertwined structures of the self-assembled dimers [2a]2 and [4a]2 were elucidated by quantum chemical 1H NMR shift calculations. 2a and 4a form extremely stable host-guest complexes with N-methylnicotinamide 8 in methanol and water as well. According to the thermodynamic parameters determined by 1H NMR titration experiments at various temperatures the self-assembly of 2a and 4a and their strong binding to NMNA 8 observed in aqueous solution are enthalpy driven (DeltaH << 0); the enthalpic driving force is partially compensated by an unfavorable entropy (TDeltaS < 0). Self-assembly and the host-guest binding are therefore beautiful examples of the nonclassical hydrophobic effect.

Based on our linear-scaling atomic orbital second-order Møller-Plesset perturbation theory (AO-MP2) method [J. Chem. Phys. 130, 064107 (2009)], we explore the use of Cholesky-decomposed pseudodensity (CDD) matrices within the Laplace formulation. Numerically significant contributions are preselected using our multipole-based integral estimates as upper bounds to two-electron integrals so that the 1/R(6) decay behavior of transformed Coulomb-type products is exploited. In addition, we combine our new CDD-MP2 method with the resolution of the identity (RI) approach. Even though the use of RI results in a method that shows a quadratic scaling behavior in the dominant steps, gains of up to one or two orders of magnitude vs. our original AO-MP2 method are observed in particular for larger basis sets.

Quantum-chemical calculations for molecular tweezers systems are presented, where the focus is not only on the recognition process in the host-guest systems, but on the self aggregation of the tweezers host as well. Such intermolecular interactions influence the corresponding NMR spectra strongly by up to 6 ppm for proton chemical shifts, since ring-current effects are particularly important. The quantum-chemical results allow one to reliably assign the spectra and to gain information both on the structure and on the importance of intra- and intermolecular interactions. In addition, we study the accuracy of a variety of density functionals for describing the present host-guest systems, where we observe a considerable underestimation of ring-current effects on (1)H NMR chemical shifts at the density functional theory (DFT) level using smaller basis sets such as 6-31G**, so that larger bases like TZP are required. This stands in contrast to the behavior of the Hartree-Fock scheme, where small basis sets, such as 6-31G**, provide reliable (1)H NMR shieldings for molecular tweezers systems.

A brief review of our linear-scaling method for atomic-orbital (AO) second-order Møller-Plesset perturbation theory (MP2) is given. The key feature of our method is the rigorous preselection of numerically significant four-center two-electron integrals based on multipole-based integral estimates (MBIE) that do not only account for the exponential coupling between the Gaussiantype basis functions forming charge distributions, but also for the 1.R coupling between the charge distributions. This coupling turns for the required integral products in AO-MP2 into at least a 1.R 4 or even a 1.R 6 decay behavior. Using MBIE we attain linear scaling, which is illustrated for DNA fragments with up to 1052 atoms and 10 674 basis functions as computed on a single processor. The largest molecule calculated in our present work at the scaled-opposite spin (SOS-) AO-MP2 level is an RNA system comprising 1664 atoms and 19 182 basis functions. Furthermore, we present results for the use of Cholesky-decomposed pseudo-density matrices in Laplace-based MP2, that offers the advantage of exploiting occupied.virtual blocking both with and without auxiliary basis sets.

Self-association of aminopyrazole peptide hybrid 1 leads to stacked nanorosettes. This remarkable, well-ordered structure obeys the laws of nucleic acid self-assembly. In a strictly hierarchical process, formation of aminopyrazole "base" triplets via a hydrogen bond network is accompanied by pi-stacking with a second rosette and final dimerization of two double rosettes to a four-layer superstructure, stabilized by a six-fold half-crown alkylammonium lock. The final complex is soluble in organic as well as in aqueous solution. It was characterized in the solid state by X-ray crystallography, in water by NMR spectroscopy, and in silico by quantum chemical shift calculation. All these methods provide strong evidence for the same hexameric complex geometry. Its structural features bear striking similarity to nucleic acid architectures and their peptidic counterparts, especially alanyl-PNA. The whole self-assembly process is highly solvent- and temperature-dependent and occurs with a high degree of cooperativity--no intermediates are observed. Formation and dissociation of the nanorosette, however, are kinetically slow. The limitation to a hexameric aggregate can be explained by six sterically demanding valine residues, whose replacement by alanines may result in formation of infinite fibers.

The implementation of the solvent macromolecule boundary potential (SMBP) by Benighaus and Thiel (J. Chem. Theory Comput. 2009, 5, 3114) into the program package CHARMM is presented. The SMBP allows for the efficient calculation of solvent effects for large macromolecules using irregularly shaped dielectric boundaries. In contrast to the generalized solvent boundary potential (GSBP) by Roux et al. (J. Chem. Phys. 2001, 114, 2924) from which it is derived, the SMBP is targeted for quantum mechanical/molecular mechanical (QM/MM) setups using ab initio methods for the QM part. After presenting benchmark results for simple model systems, applications of the SMBP for the calculation of geometries, reaction energy barriers, and vibrational frequencies for an alkaline phosphatase (AP) enzyme are discussed. Although the effect of the boundary potential on optimized structures (including the transition state) and vibrational frequencies is relatively small, the energetics of the phosphoryl transfer catalyzed by AP depend significantly on the boundary potential. Finally, to emphasize a unique feature of our implementation, we apply both SMBP and GSBP to the calculation of the energy barrier for a proton transfer reaction in a simple model channel, where the effect of an external transmembrane potential is studied. Due to the dipolar response of the polar environment, the effective charge displacement estimated based on the effect of the membrane potential on the proton transfer energetics deviates from the net charge that passes the membrane.

The broad signals in D 2 O could not be assigned by C,H-COSY. Therefore, the assignment of the signals was made by comparison with the signals in CD 3 OD. * The broad signals in D 2 O could not be assigned by C,H-COSY. Therefore, the assignment of the signals was made by comparison with the signals in CD 3 OD.

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