The Conformation of a Peptidyl Methyl Ketone Inhibitor Bound to the Human Cytomegalovirus Protease

A weak inhibitor means faster exchange! Since the methyl ketone MK2 is a weak noncovalent peptidyl inhibitor of the human cytomegalovirus protease, exchange between the free and enzyme-bound forms is rapid. This allows for the use of transferred NOE NMR methods and molecular modeling, which show that the bound conformation of MK2 is an extended peptide. This is confirmed by the results of an X-ray crystallographic analysis of a related enzyme–inhibitor complex.     

Non-perturbative effects in two-dimensional lattice O(N) models

Non-abelian analogues of Kosterlitz-Thouless vortices may have important effects in two-dimensional lattice spin systems with O(N) symmetries. Renormalization group equations which include these effects are developed in two ways. The first set of equations extends the renormalization group equations of Kosterlitz to O(N) spin systems, in a form suggested by Cardy and Hamber. The second is derived from a Villain-type O(N) model using Migdal's recursion relations. Using these equations, the part played by topological excitations in the crossover from weak to strong coupling behavior is studied. Another effect which influences crossover behavior is also discussed: irrelevant operators which occur naturally in lattice theories can make important contributions to the renormalization group flow in the crossover region. When combined with conventional perturbative results, these two effects may explain the observed crossover behavior of these models.     

Facile synthesis of isocampholenic acids by the rearrangement of camphor derivatives

A variety of substituted isocampholenic acid derivatives were prepared by rearrangement of the camphor skeleton of a variety of tertiary alcohols derived from ketopinic acid. The reaction was highly reliable and retained the stereochemical information from the camphor scaffold. This rearrangement represents an efficient way to prepare synthetically useful isocampholenic acids. Mechanistic experiments show that a short-lived carbocation is implicated in the reaction.     

Fullerol cluster formation in aqueous solutions: implications for environmental release

Here we report on the characteristics of fullerol in aqueous systems and examine those conditions that affect the physical state of fullerol in water. When dispersed in water fullerol forms polydisperse suspensions characterized by both small ( approximately 100 nm) and large associations (>500 nm). These clusters are charged with a point of zero net proton charge (PZNPC) of approximately pH 3. Though the size of fullerol clusters may be manipulated through changes in solution chemistry, principally pH, cluster formation cannot be entirely prevented through these means alone. The fullerol cluster structure is amorphous as revealed by X-ray diffraction analysis, which is in contrast to clusters of C(60) formed through dissolution in toluene and then introduced into water through sonication (SONnC(60)). The SONnC(60) clusters are crystalline with a structure similar to that of unreacted C(60) crystals.     

$\mathcal{PT}$ Symmetry in Statistical Mechanics and the Sign Problem

Generalized PT\mathcal{PT} symmetry provides crucial insight into the sign problem for two classes of models. In the case of quantum statistical models at non-zero chemical potential, the free energy density is directly related to the ground state energy of a non-Hermitian, but generalized PT\mathcal{PT}-symmetric Hamiltonian. There is a corresponding class of PT\mathcal{PT}-symmetric classical statistical mechanics models with non-Hermitian transfer matrices. We discuss a class of Z(N) spin models with explicit PT\mathcal{PT} symmetry and also the ANNNI model, which has a hidden PT\mathcal{PT} symmetry. For both quantum and classical models, the class of models with generalized PT\mathcal{PT} symmetry is precisely the class where the complex weight problem can be reduced to real weights, i.e., a sign problem. The spatial two-point functions of such models can exhibit three different behaviors: exponential decay, oscillatory decay, and periodic behavior. The latter two regions are associated with PT\mathcal{PT} symmetry breaking, where a Hamiltonian or transfer matrix has complex conjugate pairs of eigenvalues. The transition to a spatially modulated phase is associated with PT\mathcal{PT} symmetry breaking of the ground state, and is generically a first-order transition. In the region where PT\mathcal{PT} symmetry is unbroken, the sign problem can always be solved in principle using the equivalence to a Hermitian theory in this region. The ANNNI model provides an example of a model with PT\mathcal{PT} symmetry which can be simulated for all parameter values, including cases where PT\mathcal{PT} symmetry is broken.     

Intensities of line features in vibration-rotational bands 2–0 to 6–0 of NO XΠr and experimental evaluation of a radial function for electric dipolar moment

We measured the strengths of individual line-like features, representing unresolved Λ doublets, in vibration-rotational bands 2–0 to 6–0 of ¹⁴N¹⁶O within each substate of electronic ground state X²Π_1/2,3/2 in mid and near infrared regions. Analyses of these data to derive values of matrix elements for vibrational transitions enabled production of a radial function for electric dipolar moment, containing seven parameters, that satisfactorily reproduces the intensities of about 700 such features for vibrational states up to ν = 6.     

High-pt probes of the quark-gluon plasma: STAR/PHENIX results at RHIC

In this talk I review the use of scattered high-pt partons as probes of the quark-gluon plasma formed at RHIC. Recent results from both STAR and PHENIX are used to assess our current understanding of how these partons lose energy as they travel through the plasma and the extent that energy-loss can be used to extract properties of the plasma.     

Synthesis of a thymidine dinucleotide analogue containing an internucleotide silyl linkage

The synthesis of a silyl-linked analogue of a thymidine dinucleotide is described. The use of 5′-dimethoxytrityl and 3′-levulinyl protection allows mild and completely selective deprotection.