Enantiospecific First Total Synthesis of ent-Allothapsenol

The enantiospecific first total synthesis of the enantiomer of the irregular sesquiterpene from Ligusticumgrayi allothapsenol, starting from the readily available monoterpene (R)-carvone, is described, which confirmed the assumed absolute configuration of the natural product.

The substrate dependent competitive formation of cyclobutanones and cyclopentanones in an intramolecular rhodium carbenoid CH insertion reaction: enantiospecific total synthesis of silphiperfol-6-ene

The enantiospecific total synthesis of silphiperfol-6-ene has been accomplished starting from the readily available monoterpene (R)-limonene, employing a rhodium carbenoid insertion into the CH bond of a tertiary methyl group. A substrate dependent competitive insertion of the rhodium carbenoid in the gamma- and beta-CH bonds to form cyclopentanone and cyclobutanones, respectively, has been described. (C) 2012 Elsevier Ltd. All rights reserved.

Scheduling identical parallel machines with machine eligibility restrictions to minimize total weighted flowtime in automobile gear manufacturing

In this paper, we address a scheduling problem for minimizing total weighted flowtime, observed in automobile gear manufacturing. Specifically, the bottleneck operation of the pre-heat treatment stage of gear manufacturing process has been dealt with in scheduling. Many real-life scenarios like unequal release times, sequence dependent setup times, and machine eligibility restrictions have been considered. A mathematical model taking into account dynamic starting conditions has been proposed. The problem is derived to be NP-hard. To approach the problem, a few heuristic algorithms have been proposed. Based on planned computational experiments, the performance of the proposed heuristic algorithms is evaluated: (a) in comparison with optimal solution for small-size problem instances and (b) in comparison with the estimated optimal solution for large-size problem instances. Extensive computational analyses reveal that the proposed heuristic algorithms are capable of consistently yielding near-statistically estimated optimal solutions in a reasonable computational time.

Total Synthesis of (+)-Eburnamonine

The enantiospecific total synthesis of vinca alkaloid (+)-eburnamonine is accomplished from L-ethyl lactate. Key feature of the synthesis is the construction of the chiral quaternary center involving a Johnson-Claisen rearrangement and assembly of the pentacyclic core by the Pictet-Spengler reaction and ring-closing metathesis.

Total Synthesis of (+)-Cladospolide A

A stereoselective total synthesis of (+)-cladospolide A from D-ribose is described. Key features of the synthesis include olefin cross metathesis and Yamaguchi lactonization.

Detection of sugar-lectin interactions by multivalent dendritic sugar functionalized single-walled carbon nanotubes

We show that single walled carbon nanotubes (SWNTs) decorated with sugar functionalized poly (propyl ether imine) (PETIM) dendrimer is a very sensitive platform to quantitatively detect carbohydrate recognizing proteins, namely, lectins. The changes in electrical conductivity of SWNT in field effect transistor device due to carbohydrate-protein interactions form the basis of present study. The mannose sugar attached PETIM dendrimers undergo charge-transfer interactions with the SWNTs. The changes in the conductance of the dendritic sugar functionalized SWNT after addition of lectins in varying concentrations were found to follow the Langmuir type isotherm, giving the concanavalin A (Con A)-mannose affinity constant to be 8.5 x 10(6) M-1. The increase in the device conductance observed after adding 10 nM of Con A is same as after adding 20 mu M of a non-specific lectin peanut agglutinin, showing the high specificity of the Con A-mannose interactions. The specificity of sugar-lectin interactions was characterized further by observing significant shifts in Raman modes of the SWNTs. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4739793]

Total synthesis of (+)-phomopsolide B

An enantiospecific total synthesis of polyhydroxy delta-pyrone natural product phomopsolide B is accomplished. The main feature of the synthesis is the installation of the required E-olefin by Horner-Emmons-Wordsworth reaction and the formation of the lactone involving Still-Gennari olefination followed by lactonization. (C) 2012 Elsevier Ltd. All rights reserved.

2,3-Unsaturated enoses. A Pummerer rearrangement route to sugar vinyl sulfides and synthesis of 3-deoxy-3-alkyl/arylsulfinyl pyranosides

A Pummerer rearrangement of 2,3-dideoxy-3-alkyl/arylsulfinyl-arabino-hexopyranosides is reported. Treatment of sulfinyl-arabino-hexopyranoside derivatives, obtained through oxidation of the corresponding thio-derivatives, with trifluoroacetic anhydride (TFAA)/pyridine led to a facile formation of 2,3-dideoxy-3-alkyl/arylthio-hex-2-enopyranosides. Upon conversion of sugar vinyl sulfides to vinyl sulfoxides, conjugate addition reactions were conducted with alkoxides, to afford 3-deoxy-3-alkyl/arylsulfinyl pyranosides, in the manno-configuration exclusively. Whereas the conjugate addition reaction did not proceed with ether protecting groups, ester protecting groups and free hydroxyl groups in the sugar vinyl sulfoxide permitted the reaction. (C) 2012 Elsevier Ltd. All rights reserved.

Algorithmic aspects of k-tuple total domination in graphs

For a fixed positive integer k, a k-tuple total dominating set of a graph G = (V. E) is a subset T D-k of V such that every vertex in V is adjacent to at least k vertices of T Dk. In minimum k-tuple total dominating set problem (MIN k-TUPLE TOTAL DOM SET), it is required to find a k-tuple total dominating set of minimum cardinality and DECIDE MIN k-TUPLE TOTAL DOM SET is the decision version of MIN k-TUPLE TOTAL DOM SET problem. In this paper, we show that DECIDE MIN k-TUPLE TOTAL DOM SET is NP-complete for split graphs, doubly chordal graphs and bipartite graphs. For chordal bipartite graphs, we show that MIN k-TUPLE TOTAL DOM SET can be solved in polynomial time. We also propose some hardness results and approximation algorithms for MIN k-TUPLE TOTAL DOM SET problem. (c) 2012 Elsevier B.V. All rights reserved.

An Approach to seco-Prezizaane Sesquiterpenoids: Enantioselective Total Synthesis of (+)-1S-Minwanenone

A strategy of general applicability toward seco-prezizaane sesquiterpenes, from a chiral, tricyclic synthon, readily available via an enzymatic resolution step from the Diels-Alder adduct of cyclopentadiene and p-benzoquinone, has been devised. Our approach enables harnessing of the stereochemical proclivities of the norbornyl system to install the desired stereochemistry at the key stereogenic centers. Recourse to an interesting stratagem to realign a stereochemical divergence into stereoreconvergence forms the cornerstone of our successful approach. The first total synthesis of (+)-1S-minwanenone, a prototypical member of seco-prezizaane subclass, has been accomplished.

GFT projection NMR for efficient H-1/C-13 sugar spin system identification in nucleic acids

A newly implemented G-matrix Fourier transform (GFT) (4,3)D HC(C)CH experiment is presented in conjunction with (4,3)D HCCH to efficiently identify H-1/C-13 sugar spin systems in C-13 labeled nucleic acids. This experiment enables rapid collection of highly resolved relay 4D HC(C)CH spectral information, that is, shift correlations of C-13-H-1 groups separated by two carbon bonds. For RNA, (4,3)D HC(C)CH takes advantage of the comparably favorable 1'- and 3'-CH signal dispersion for complete spin system identification including 5'-CH. The (4,3)D HC(C)CH/HCCH based strategy is exemplified for the 30-nucleotide 3'-untranslated region of the pre-mRNA of human U1A protein.

Enantiospecific Total Synthesis of (-)-Bengamide E

Total synthesis of the polyhydroxy caprolactam amide natural product, bengamide E, is accomplished starting from tartaric acid. Key reactions in the synthesis include desymmetrization of the bis(dimethylamide) unit of tartaric acid, Zn(BH4)2-mediated anti-selective reduction, and a HornerWadsworthEmmons olefination.

QCD mini-jets contribution to the total cross-section for pions and protons and expectations at LHC

We describe our kt-resummation model for total cross-sections and show its application to pp and ¯pp scattering. The model uses mini-jets to drive the rise of the cross-section and soft gluon resummation in the infrared region to transform the violent rise of the mini-jet cross-section into a logarithmic behaviour in agreement with the Froissart bound.

An Expeditious Enantiospecific Total Synthesis of (-)-Crassalactone C

A concise and expeditious approach for the total synthesis of bioactive styryllactone (-)-crassalactone C is presented from tartaric acid. The main features of the synthesis include the desymmetrization of dimethylamide of tartaric acid and the effective use of cinnamoyl ester as a protecting group as well as a reactant in the ring-closing metathesis reaction.

Role of invariant water molecules and water-mediated ionic interactions in D-xylose isomerase from Streptomyces rubiginosus

The enzyme, D-xylose isomerase (D-xylose keto-isomerase; EC 5.3.1.5) is a soluble enzyme that catalyzes the conversion of the aldo-sugar D-xylose to the keto-sugar D-xylulose. A total of 27 subunits of D-xylose isomerase from Streptomyces rubiginosus were analyzed in order to identify the invariant water molecules and their water-mediated ionic interactions. A total of 70 water molecules were found to be invariant. The structural and/or functional roles of these water molecules have been discussed. These invariant water molecules and their ionic interactions may be involved in maintaining the structural stability of the enzyme D-xylose isomerase. Fifty-eight of the 70 invariant water molecules (83%) have at least one interaction with the main chain polar atom.