Pentopyranosyl Oligonucleotide Systems. 9th Communication

Pyranosyl‐RNA (‘p‐RNA’ ) is an oligonucleotide system isomeric to natural RNA and composed of the very same building blocks as RNA. Its generational, chemical, and informational properties are deemed to be those of an alternative nucleic acid system that could have been a candidate in Nature's evolutionary choice of the molecular basis of genetic function. We consider the study of the chemistry of p‐RNA as etiologically relevant in the sense that knowledge of its structural, chemical, and informational properties on the chemical level offers both a perspective and reference points for the recognition of specific structural assets of the RNA structure that made it the (supposedly) superior system among possible alternatives and, therefore, the system that became part of biology as we know it today. The paper describes the chemical synthesis of β‐d‐ (and L )‐ribopyranosyl‐(4′→2′)‐oligonucleotide sequences, presents a resume of their structural and chemical properties, and cautiously discusses what we may and may not have learned from the pyranosyl isomer of RNA with respect to the conundrum of RNA's origin.     

On the departure process of a leaky bucket system with long-range dependent input traffic

Due to the strong experimental evidence that the traffic to be offered to future broadband networks will display long-range dependence, it is important to study the possible implications that such traffic may have for the design and performance of these networks. In particular, an important question is whether the offered traffic preserves its long-range dependent nature after passing through a policing mechanism at the interface of the network. One of the proposed solutions for flow control in the context of the emerging ATM standard is the so-called leaky bucket scheme. In this paper we consider a leaky bucket system with long-range dependent input traffic. We adopt the following popular model for long-range dependent traffic: Time is discrete. At each unit time a random number of sessions is initiated, having the distribution of a Poisson random variable with mean λ. Each of these sessions has a random duration τ, where the integer random variable τ has finite mean, infinite variance, and a regularly varying tail, i.e., P(τ >К) ~ К^-Lα L(К), where 1 < α < 2 L(·) is a slowly varying function. Once a session is initiated, it generates one cell at each unit of time until its termination. We examine the departure process of the leaky bucket policing mechanism driven by such an arrival process, and show that it too is long-range dependent for any token buffer size and any - finite or infinite - cell buffer size. Moreover, upper and lower bounds for the covariance sequence of the output process are established. The above results demonstrate that long-range dependence cannot be removed by the kinds of flow control schemes that are currently being envisioned for broadband networks. This revised version was published online in June 2006 with corrections to the Cover Date.     

Asymmetric synthesis of 6-(2′,3′,4′,5′,6′-pentafluorophenyl)-δ-lactones via “allyl”boranes: application for the synthesis of fluorinated analog of key pharmacophore of statin drugs

Asymmetric “allyl”boration of pentafluorobenzaldehyde with various α-pinene based “allyl”boranes provides homoallylic alcohols in high de and ee; the alcohols have been converted into δ-lactones via acryloylation, ring-closing metathesis and hydrogenation. Pentafluorophenyl analog of key pharmacophore of statin drugs has been synthesized using diastereoselective epoxidation and regioselective reduction as key steps.     

Tuning size and catalytic activity of nano-clusters of cobalt oxide

Cobalt oxides were prepared by three different methods: (1) by reacting cobalt nitrate with oxalic acid, (2) co-precipitating cobalt nitrate with sodium carbonate, and (3) using sodium dodecyl sulphate as organic surfactant. All three samples were characterized before and after calcination by solvent extraction and the resulting products examined by IR spectroscopy. In the case of method 3, the removal of surfactant was followed by TGA studies. Products from all three methods were identified by XRD. Peaks in low angle XRD indicate the porous nature of the oxides. The morphology of the pores was studied by transmission electron microscopy. Some irregular pore structures were obtained for samples from methods 1 and 2, with an average size of 4–6 nm. Only the product from method 3 using SDS as template showed ordered structure and optimum size, and Brunauer-Emmet-Teller surface areas of the as-prepared, as well as the treated samples, exhibited H3 type hysteresis. The samples from the three methods were used as catalysts in the oxidation reaction of cyclohexane under mild conditions and the catalytic efficiency of the cobalt oxide was comparable with mesoporous cobalt oxides.     

Colossal magnetoresistance manganites: A new approach

Manganites of the LA_1−x Ca _x MnO₃ family show a variety of new and poorly understood electronic, magnetic and structural effects. Here we outline a new approach recently proposed by us, where we argue that due to strong Jahn-Teller (JT) coupling with phonons the twofold degeneratee _g states at the Mn sites dynamically reorganize themselves into localised, JT polaronsl with exponentially small inter-site hopping, and band-like, nonpolaronic statesb, leading to anew 2-band model for manganites which includes strong Coulomb and Hund’s couplings. We also discuss some results from a dynamical mean-field theory treatment of the model which explains quantitatively a wide variety of experimental results, including insulator-metal transitions and CMR, in terms of the influence of physical conditions on the relative energies and occupation of thel andb states. We argue that this microscopic coexistence of the two types of electronic states, and their relative occupation and spatial correlation is the key to manganite physics. Dedicated to Professor C N R Rao on his 70th birthday     

Expedient synthesis of substituted imidazoles from nitriles

Expedient and practical new methodology for the synthesis of substituted imidazoles was developed to provide a rapid access to a variety of 2-substituted, 1,2-disubstituted and 1,2,4-trisubstituted imidazoles by the direct CuCl-mediated reaction of nitriles with α-amino acetals in an intermolecular as well as intramolecular fashion.     

Broadband and band-selective IMPRESS-gHMBC: compensation of refocusing inefficiency with synchronized inversion sweep

Compensation of refocusing inefficiency in a gHMBC experiment by replacing the rectangular pi pulse with a pair of adiabatic pulses with synchronized inversion sweep (CRISIS) significantly improves the performance of the gHMBC experiment. The CRISIS-gHMBC experiment retains the pure absorptive shapes in F1 and hence results in better lineshape and higher resolution than the current versions of magnitude mode gHMBC spectra. When used as a broadband experiment, CRISIS-gHMBC, owing to better refocusing efficiency of the adiabatic pulse pairs, gives improved performance across the 13C spectral width. Moreover, it is shown that CRISIS-gHMBC is a robust and improved alternative and when used along with the IMPRESS (Improved Resolution using Symmetrically Shifted pulses) technique further increases the sensitivity and resolution without additional experimental time. The IMPRESS-CRISIS combination is demonstrated for broadband gHMBC and band-selective gHMBC experiments. The ICbs-gHMBC [IMPRESS-CRISIS-band-selective gHMBC] experiment is an attractive and better alternative to individual band-selective gHMBC.     

Mass spectral investigations on trichothecene mycotoxins. III. Synthesis, characterization and applications of pentafluoropropionyl and trifluoroacetyl esters of simple trichothecenes

The pentafluoropropionyl, (PFP) and trifluoroacetyl (TFA) esters of several naturally occurring and synthetically modified simple trichothecenes were synthesized in nanogram amounts and characterized. Optimum conditions for the gas chromatographic (GC) separation of these derivatives and their analysis by negative ion chemical ionization (NICI) mass spectrometric technique were determined. These perfluoroacyl derivatives under the NICI conditions undergo limited but characteristic fragmentations similar to the fragmentations of heptafluorobutyryl esters of trichothecenes under the same conditions. Characteristic ions for the specific detection and accurate quantification of these PFP and TFA derivatives were chosen. Preliminary results indicated that the PFP derivatives are better suited for the analysis of simple trichothecenes by GC-NICI-MS technique. Ultra trace (0.5-2.0 pg) amounts of these PFP derivatives were detected by the developed procedure.     

A highly efficient and general N-monomethylation of functionalized primary amines via formylation--borane:methyl sulfide reduction

Formylation of functionalized primary aromatic and aliphatic amines with acetic formic anhydride (AFA) followed by borane:methyl sulfide reduction in the same pot affords the corresponding $\text{N}$-methylamines in excellent isolated yields, uncontaminated bybis alkylation; the reaction sequence is applicable to even very weakly basic and sterically hindered amines.