Crystal engineering of metalloporphyrin assemblies. New supramolecular architectures mediated by bipyridyl ligands

Targeted synthesis of new supramolecular motifs of metalloporphyrins in crystals by a concerted mechanism of molecular recognition in three dimensions, aided by organic ligands, is presented; it involves induced assembly of [tetrakis(4-hydroxyphenyl)porphyrinato]zinc species by a combination of axial coordination through bridging bipyridyls and of lateral hydrogen bonding.     

Practical Methods for Solid-State NMR Distance Measurements on Large Biomolecules: Constant-Time Rotational Resonance

Simple modifications of the rotational resonance experiment substantially reduce the total experimental time needed to measure weak homonuclear dipolar couplings, a critical factor for achieving routine internuclear distance measurements in large biomolecular systems. These modifications also address several problems cited in the literature. Here we introduce a constant-time rotational resonance experiment that eliminates the need for control spectra to correct for effects from variable RF heating, particularly critical for accurate long-distance measurements. This reduces the total number of experiments needed by as much as a factor of 2. Other improvements incorporated include achieving selective inversion with a delay rather than a weak pulse (P. R. Costa et al., J. Am. Chem. Soc. 119, 10487-10493, 1997), which we observe results in the elimination of oscillations in peak intensities for short mixing time points. This reduces the total experiment time in two ways. First, there is no longer a need to average different "zero"-time points (S. O. Smith et al., Biochemistry 33, 6334-6341, 1994) to correct for intensity variations. Second, short-mixing-time lineshape differences observed in large membrane-bound proteins only appear with the weak-pulse inversion and not when using the delay inversion. Consistent lineshapes between short and long mixing times permit the use of a single spectrum for subtraction of natural abundance background signals from all labeled-protein time points. Elimination of these effects improves the accuracy and efficiency of rotational resonance internuclear distance measurements.     

Metal-stabilized phenoxonium cation

An unprecedented metal-stabilized phenoxonium cation was prepared by a process involving dearomatization of a phenoxy complex. The unique eta2 C=O-metal (iridium) coordination mode leaves the positive charge delocalized within the former aromatic ring. The X-ray structure and conversion into eta2 C=O-coordinated metal-quinone complex are described.     

Self-Concordant Barriers for Convex Approximations of Structured Convex Sets

We show how to approximate the feasible region of structured convex optimization problems by a family of convex sets with explicitly given and efficient (if the accuracy of the approximation is moderate) self-concordant barriers. This approach extends the reach of the modern theory of interior-point methods, and lays the foundation for new ways to treat structured convex optimization problems with a very large number of constraints. Moreover, our approach provides a strong connection from the theory of self-concordant barriers to the combinatorial optimization literature on solving packing and covering problems.     

Steric and Electronic Effects on an Antibody‐Catalyzed Diels–Alder Reaction

A series of substituted thiophene dioxides was tested as diene substrates for the antibody 1E9, which was elicited with a hexachloronorbornene derivative and normally catalyzes the inverse electron‐demand Diels–Alder reaction between 2,3,4,5‐tetrachlorothiophene dioxide (TCTD) and N‐ethylmaleimide (NEM). Previous structural and computational studies had suggested that the catalytic efficiency of this system derives in part from a very snug fit between the apolar active site and the transition state of this reaction. Nevertheless, replacing all the Cl‐atoms in the hapten with Br‐atoms leads to no loss in affinity (K_d=0.1 nM ), indicating substantial conformational flexibility in the residues that line the binding pocket. Consistent with this observation, the 2,3,4,5‐tetrabromothiophene dioxide is a good substrate for the antibody (k_cat=1.8 min^?1, K_NEM=14 μM ), despite being considerably larger than TCTD. In contrast, normal electron‐demand Diels–Alder reactions between NEM and unsubstituted thiophene dioxide or 2,3,4,5‐tetramethylthiophene dioxide, which are much smaller or nearly isosteric with TCTD, respectively, are not detectably accelerated. These results show that the electronic properties of the 1E9 active site are optimized to a remarkable degree for the inverse electron‐demand Diels–Alder reaction for which it was designed. Indeed, they appear to play a more important role in catalysis than simple proximity effects.     

Primal Central Paths and Riemannian Distances for Convex Sets

In this paper, we study the Riemannian length of the primal central path in a convex set computed with respect to the local metric defined by a self-concordant function. Despite some negative examples, in many important situations, the length of this path is quite close to the length of a geodesic curve. We show that in the case of a bounded convex set endowed with a ν-self-concordant barrier, the length of the central path is within a factor O(ν ^1/4) of the length of the shortest geodesic curve. This paper presents research results of the Belgian Program on Interuniversity Poles of Attraction initiated by the Belgian State, Prime Minister’s Office, Science Policy Programming.     

Solvability of a Class of Braided Fusion Categories

We show that a weakly integral braided fusion category ${{\mathcal C}}$ such that every simple object of ${{\mathcal C}}$ has Frobenius-Perron dimension ≤?2 is solvable. In addition, we prove that such a fusion category is group-theoretical in the extreme case where the universal grading group of ${{\mathcal C}}$ is trivial.     

Soy addition improves the texture of microwavable par-baked pocket-type flat doughs

Microwavable baked goods are used frequently by the food industry to enrobe meat, vegetable, and sweet items for convenient meal delivery but suffer from poor texture upon microwave re-heating. Par-baking the dough prior to the reheating stage provides an opportunity to supply fresh baked goods with a simple baking stage at retail locations. Nonetheless, reheating conditions significantly affect texture of reheated par-baked products, resulting in shrinkage, porosity reduction, and crust softening. Appropriate formula modifications have been shown to reduce microwave-induced toughness of reheated bread by virtue of water-binding agents and lipids. The objective of this study was, therefore, to assess the effect of soy addition on the water state of microwavable par-baked doughs. Four dough formulations were developed by substituting wheat flour with increasing amounts of a soy blend. Addition of soy at 20 and 26% levels improved textural properties of microwaved products, resulting in a softer and less chewy texture. Thermogravimetric analysis (TG) showed increased water binding in soy formulations 20 and 26% with a broadening of the main peak (attributed to water loss) that shifted from 40 to 80 °C. Differential scanning calorimetry (DSC) depicted a transition in the −25/−10 °C range, attributed to soy lipids melting, which broadened at high soy addition. This change in water dynamics was confirmed by proton nuclear magnetic resonance (¹H NMR) relaxation tests, T ₁ and T ₂, having lower values in soy products, and therefore, depicting a more solid-like matrix. Soy addition above 20% significantly improved the texture of microwave reheated par-baked flat doughs.     

Dynamic storage allocation with known durations

This paper is concerned with a new version of on-line storage allocation in which the durations of all processes are known at their arrival time. This version of the problem is motivated by applications in communication networks and has not been studied previously. We provide an on-line algorithm for the problem with a competitive ratio of O(min{log Δ,log τ}), where Δ is the ratio between the longest and shortest duration of a process, and τ is the maximum number of concurrent active processes that have different durations. For the special case where all durations are powers of two, the competitive ratio achieved is O(loglog Δ).