Total syntheses of 28,29-diepi-arenamide A, 29-epi-arenamide A, and 28-epi-arenamide A

This communication describes the synthesis of stereochemical analogs of arenamide A, a 19-membered cytotoxic depsipeptide isolated from the fermentation broth of a marine bacterial strain Salinispora arenicola. The key steps are diastereoselective aldol reaction, Mitsunobu reaction, and HATU mediated macrolactamization.     

Spectrophotometric Investigation of the Charge–Transfer Interaction of 2,3-Dicyano-1,4-naphthoquinone with N-Ethylaniline in Chlorinated Solvents

The charge?Ctransfer interaction between 2,3-dicyano-1,4-naphthoquinone (DCNQ) and N-ethylaniline was studied in the halocarbons chloroform and dichloromethane and a 1:1 (v/v) mixture of these two solvents. A rapid interaction between DCNQ and N-ethylaniline results in the formation of the monosubstituted final product. The reaction is found to proceed through an initial charge?Ctransfer (CT) complex intermediate. The equilibrium constants of the ??-complex, in all the three media, were evaluated along with first-order and second-order rate constants for the appearance and disappearance of the ??- and ??-complexes. The final product was isolated and characterized by IR, NMR and elemental analysis. Based on the kinetic results a mechanism was proposed for the reaction.     

Ionic liquid/PPh3 promoted cleavage of diphenyl disulfide and diselenide: a straight-forward metal-free one-pot route to the synthesis of unsymmetrical sulfides and selenides

A metal-free cleavage of diphenyl disulfide and diphenyl diselenide has been achieved using ionic liquid/triphenyl phosphine (PPh₃) and a convenient protocol for the one-pot synthesis of unsymmetrical sulfides and selenides by condensing ‘in situ’ generated thiolate or selenate anion with alkyl halides has been developed. In addition, 1,4-conjugate addition of the generated thiolate anions to activated alkenes has also been demonstrated. The ionic liquid, 1-methyl-3-pentyl imidazolium bromide, [pmIm]Br plays a crucial role in promoting the course of the reactions and shows superior activity and selectivity compared to other solvents. The [pmIm]Br has been reused for at least five times without appreciable loss of activity.     

Catalytic Activity and Morphological Properties of Ni/MgO Catalysts for the Oxidative Coupling of Methane

The catalytic activity of Ni/MgO catalysts was studied for the oxidative coupling of methane (OCM). The catalysts were characterized using transmission electron microscope (TEM) and XRD. The increase in C2+ selectivity of Ni/MgO was attributed to the presence of bulk dislocations and MgNiO₂ phase. This revised version was published online in June 2006 with corrections to the Cover Date.     

Rectangular Tiling in Multidimensional Arrays

We study the following tiling problem in d dimensions: given a d-dimensional rectangular array of nonnegative numbers and an integer p, partition the array into at most p rectangular subarrays so that the maximum weight of any subarray is minimized; the weight of a subarray is the sum of its elements. The rectangular tiling problem is motivated by applications in data mining, data partitioning, and video compression. Recently, Khanna, Muthukrishnan, and Paterson [SODA '98], showed that the tiling problem is NP-complete and gave a 2.5-approximation algorithm for d = 2.In this paper, we extend their result to multidimensional arrays and give an algorithm with approximation ratio , for d ≥ 2. The algorithm can be implemented to run in worst-case time O(N + p log N) time, where N is the size of the array, and the constant is of the order d!. We also obtain a similar algorithm for the dual tiling problem, where the goal is to compute a tiling of weight at most W using as few tiles as possible. Our algorithm yields an approximation factor (2d + 1).We implemented our algorithm and ran simulation tests on multidimensional arrays with random data. In our limited experiments, the algorithm always produced approximations that were no worse than factor two from the optimal.     

Polyphenolic Profiling,Antioxidant, and Antimicrobial Activities Revealed the Quality and Adaptive Behavior of Viola Species,a Dietary Spice in the Himalayas

Background: Himalayan Viola species (Banksha) are traditionally important herbs with versatile therapeutic benefits such as antitussive, analgesic, antipyretic, antimalarial, anti-inflammatory, and anticancerous ones. The current investigation was focused on exploring polyphenolic profiles, antioxidant, and antimicrobial potentials of wild viola species at 15 gradient locations (375–1829 m). Methods: Morphological, physiochemical, and proximate analyses were carried out as per WHO guidelines for plant drug standardization. Total polyphenolic and flavonoid content were carried out using gallic acid and rutin equivalent. UPLC-DAD was used to profile the targeted polyphenols (gallic acid, vanillic acid, syringic acid, p-coumaric acid, ferulic acid, rutin, quercetin, luteolin, caffeic acid, and epicatechin). Similarly, all samples were screened for antioxidant and antimicrobial activity. Statistical analysis was used to correlate polyphenolic and targeted activities to assess Viola species adaptation behavior patterns. Results: Viola canescens (V. canescens) and Viola pilosa (V. pilosa) were found abundantly at their respective sites. Among flowers and leaves, flowers of V. canescens and V. pilosa showed higher total polyphenolic and flavonoid content (51.4 ± 1.13 mg GAE/g and 65.05 ± 0.85 mg RE/g, and 33.26 ± 0.62 mg GAE/g and 36.10 ± 1.41 mg RE/g, respectively). Furthermore, UPLC-DAD showed the uppermost content of p-coumaric acid in flowers and ferulic acid in leaves, while rutin was significant in both the tissues. Conclusions: The adaptive behavior of Viola species showed variability in morphological characters with the altitudes, while targeted polyphenols and activities were significant at mid-altitudes. This research helps in the selection of right chemotype for agrotechnological interventions and the development of nutraceutical products.     

Off-Line Maintenance of Planar Configurations

We achieve anO(log n) amortized time bound per operation for the off-line version of the dynamic convex hull problem in the plane. In this problem, a sequence ofninsert,delete, andqueryinstructions are to be processed, where each insert instruction adds a new point to the set, each delete instruction removes an existing point, and each query requests a standard convex hull search. We process the entire sequence in totalO(n log n) time andO(n) space. Alternatively, we can preprocess a sequence ofninsertions and deletions inO(n log n) time and space, then answer queries in history inO(log n) time apiece (a query in history means a query comes with a time parametert, and it must be answered with respect to the convex hull present at timet). The same bounds also hold for the off-line maintenance of several related structures, such as the maximal vectors, the intersection of half-planes, and the kernel of a polygon. Achieving anO(log n) per-operation time bound for theon-lineversions of these problems is a longstanding open problem in computational geometry.     

A Three-Stage Quantum Cryptography Protocol

We present a three-stage quantum cryptographic protocol based on public key cryptography in which each party uses its own secret key. Unlike the BB84 protocol, where the qubits are transmitted in only one direction and classical information exchanged thereafter, the communication in the proposed protocol remains quantum in each stage. A related system of key distribution is also described.