Bridged ring systems—VIII A novel ring expansion reaction

Acid treatment of 2-(β-Benzoylethyl)-cyclopentanone (III) leads directly to a phenylcycloheptene carboxylic acid (VII) and the related lactone (XI), via a bicyclic intermediate.     

Sporolides A and B: structurally unprecedented halogenated macrolides from the marine actinomycete Salinispora tropica

[structure: see text] Analysis of the fermentation broth of a strain of the marine actinomycete Salinispora tropica has led to the isolation of two unprecedented macrolides, sporolides A (1) and B (2). The structures and absolute stereochemistries of both metabolites were elucidated using a combination of NMR spectroscopy and X-ray crystallography.     

Si doped GaAs/AlGaAs terahertz detector and phonon effect on the responsivity

Terahertz detection capability of an n-type heterojunction interfacial work function internal photoemission (HEIWIP) detector is demonstrated. Threshold frequency, f₀, of 3.2 THz (93 μm) was obtained by using n-type GaAs emitter doped to 1 × 10¹⁸ cm⁻³ and Al_0.04Ga_0.96As single barrier structure. The detector shows a broad spectral response from 30 to 3.2 THz (10–93 μm) with peak responsivity of 6.5 A/W at 7.1 THz under a forward bias field of 0.7 kV/cm at 6 K. The peak quantum efficiency and peak detectivity are 19% and 5.5 × 10⁸ Jones, respectively under a bias field of 0.7 kV/cm at 6 K. In addition, the detector can be operated up to 25 K.     

On connected dominating sets of restricted diameter

A connected dominating set (CDS) is commonly used to model a virtual backbone of a wireless network. To bound the distance that information must travel through the network, we explicitly restrict the diameter of a CDS to be no more than s leading to the concept of a dominating s-club. We prove that for any fixed positive integer s it is NP-complete to determine if a graph has a dominating s  -club, even when the graph has diameter s+1$s+1$. As a special case it is NP-complete to determine if a graph of diameter two has a dominating clique. We then propose a compact integer programming formulation for the related minimization problem, enhance the approach with variable fixing rules and valid inequalities, and present computational results.     

Solving maximum clique in sparse graphs: an O(nm+n2^{d/4}) algorithm for d-degenerate graphs

We describe an algorithm for the maximum clique problem that is parameterized by the graph’s degeneracy \(d\) . The algorithm runs in \(O\left( nm+n T_d \right) \) time, where \(T_d\) is the time to solve the maximum clique problem in an arbitrary graph on \(d\) vertices. The best bound as of now is \(T_d=O(2^{d/4})\) by Robson. This shows that the maximum clique problem is solvable in \(O(nm)\) time in graphs for which \(d \le 4 \log _2 m + O(1)\) . The analysis of the algorithm’s runtime is simple; the algorithm is easy to implement when given a subroutine for solving maximum clique in small graphs; it is easy to parallelize. In the case of Bianconi-Marsili power-law random graphs, it runs in \(2^{O(\sqrt{n})}\) time with high probability. We extend the approach for a graph invariant based on common neighbors, generating a second algorithm that has a smaller exponent at the cost of a larger polynomial factor.     

n-Type GaAs/AlGaAs heterostructure detector with a 3.2 THz threshold frequency

Terahertz detection using the free-carrier absorption requires a small internal work function of the order of a few millielectron volts. A threshold frequency of 3.2 THz (93 microm or approximately 13 meV work function) is demonstrated by using a 1 x 10(18) cm(-3) Si-doped GaAs emitter and an undoped Al(0.04)Ga(0.96)As barrier structure. The peak responsivity of 6.5 A/W, detectivity of 5.5 x 10(8) Jones, and quantum efficiency of 19% were obtained at 7.1 THz under a bias field of 0.7 kV/cm at 6 K, while the detector spectral response range spans from 3.2 to 30 THz.     

On imposing connectivity constraints in integer programs

We study an extension of the classical graph cut problem, wherein we replace the modular (sum of edge weights) cost function by a submodular set function defined over graph edges. Special cases of this problem have appeared in different applications in signal processing, machine learning, and computer vision. In this paper, we connect these applications via the generic formulation of “cooperative graph cuts”, for which we study complexity, algorithms, and connections to polymatroidal network flows. Finally, we compare the proposed algorithms empirically.     

Competition between amide stacking and intramolecular H bonds in γ-peptide derivatives: controlling nearest-neighbor preferences

Resonant two-photon ionization (R2PI), IR-UV holeburning (IR-UV), and resonant ion-dip infrared spectroscopy (RIDIRS) have been used to record mass-selected, single-conformation ultraviolet and infrared spectra of three simple diamide derivatives of γ-amino acids as isolated molecules cooled in a supersonic expansion. This work builds on an earlier study of Ac-γ(2)-hPhe-NHMe (James, W. H., III, et al. J. Am. Chem. Soc. 2009, 131, 14243), which showed that this methyl-capped γ-peptide forms amide-stacked conformations that are similar in stability to H-bonded conformations containing a C9 ring and more stable than C7 H-bonded ring structures. Among the γ-peptides discussed here, Ac-γ(2)-hPhe-N(Me)(2) contains an additional methyl group relative to the previously studied Ac-γ(2)-hPhe-NHMe and therefore lacks the amide NH group responsible for C9 ring formation. Three conformations of Ac-γ(2)-hPhe-N(Me)(2) are observed, all of which are amide-stacked structures. In a second new molecule, Ac-γ(2)-hPhe-NH(iPr), the C-terminal NHMe group of Ac-γ(2)-hPhe-NHMe is replaced with an NH(iPr) group. Three conformations of Ac-γ(2)-hPhe-NH(iPr) are observed, all of which are C9 H-bonded structures. The dramatic difference between C-terminal NHMe and NH(iPr) reveals the delicate balance of noncovalent forces within these γ-peptides. The third molecule we examined is a gabapentin-derived diamide (designated 1), which contains a phenylacyl group at the N-terminus and an N(Me)(2) group at the C-terminus; the latter precludes C9 H bonding. Comparison of 1 with Ac-γ(2)-hPhe-N(Me)(2) allows us to examine the impact of the backbone substitution pattern (monosubstitution at carbon-2 vs disubstitution at carbon-3) on the competition between the C7 H-bonded and the amide-stacked conformation. In this case, only C7 rings are observed. The different gas-phase behaviors observed among the molecules analyzed here offer insight on the intrinsic conformational propensities of the γ-peptide backbone, information that provides a foundation for future foldamer design efforts.