A facile entry to macrocyclic disulfides: an efficient synthesis of redox-switched crown ethers

An interesting sulfur transfer reaction with benzyltriethylammonium tetrathiomolybdate has been used efficiently for the synthesis of macrocyclic disulfides. This methodology has been extended to a high-yield synthesis of ''redox-switched'' crown ethers which have potential application for selective ion transport across liquid membranes.

A novel double friedel-crafts reaction: A new entry into bicyclo[3.2.2]nonane system

A novel synthesis of dibenzobicyclo[3.2.2]nonane systems is described through a double Friedel-Crafts reaction.

Construction of energy-level diagram of oriented benzene using connectivity information obtained by modified z-cosy experiment

Experiments involving selective perturbation of a transition yield information about the directly connected transitions, which in turn yield information for deriving the parameters of the spin Hamiltonian of oriented molecules. Problems involved with selective perturbation are removed by the use of a two-dimensional experiment, namely, the modified Z-COSY-experiment, The use of this experiment is demonstrated for obtaining the connectivity information and for determining the parameters of the spin Hamiltonian of oriented benzene, a strongly coupled six-spin system

A Sub-Nyquist Sampling Method For Computing The Level-crossing-times Of An Analog Signal: Theory And Applications

We address the problem of computing the level-crossings of an analog signal from samples measured on a uniform grid. Such a problem is important, for example, in multilevel analog-to-digital (A/D) converters. The first operation in such sampling modalities is a comparator, which gives rise to a bilevel waveform. Since bilevel signals are not bandlimited, measuring the level-crossing times exactly becomes impractical within the conventional framework of Shannon sampling. In this paper, we propose a novel sub-Nyquist sampling technique for making measurements on a uniform grid and thereby for exactly computing the level-crossing times from those samples. The computational complexity of the technique is low and comprises simple arithmetic operations. We also present a finite-rate-of-innovation sampling perspective of the proposed approach and also show how exponential splines fit in naturally into the proposed sampling framework. We also discuss some concrete practical applications of the sampling technique.

High level stable expression of rat brain type IIA sodium channel ?-subunit in CHO cells

The neuronal sodium channels are responsible for the rising phase of action potential and are composed of three subunits, of which the alpha-subunit has been shown to be adequate for most of its functional properties. We have stably expressed the rat brain type IIA sodium channel alpha-subunit in CHO cell tine using a CMV promoter-based vector. The expression was confirmed by detecting a 6.5 kb RNA corresponding to sodium channel alpha-subunit using Northern hybridization. The cells stably expressing the alpha-subunit, yield isolated sodium currents of amplitudes greater than 4nA when studied in whole-cell configuration of the patch-clamp technique. The sodium currents are characterized by activation and inactivation properties similar to neuronal sodium channels, and are blocked by the voltage gated sodium channel blocker tetrodotoxin (TTX).

Intracellular free calcium level and its response to cAMP stimulation in developing Dictyostelium cells transformed with jellyfish apoaequorin CDNA

A new method is described for measuring intracellular free calcium concentrations, [(Ca2+)(i)], in the cells of Dictyostelium discoideum transformed with apoaequorin cDNA of the jellyfish, Aequorea victoria. Aequorin, a calcium-specific indicator, was regenerated in vivo from apoaequorin produced in the cells by incubation with coelenterazine. The results showed that [(Ca2+)(i)] in developing cells markedly increases at the aggregation stage and again at the culmination stage after a temporary drop at the migration stage. Except for the vegetative stage, the cells al all stages of development exhibit a sharp transient increase in [(Ca2+)(i)] upon stimulation with a cAMP (50 nM) pulse, high responses being observed at the migration and culmination stages. Separated prestalk cells of migrating slugs contain more than twice as much [(Ca2+)(i)] and show three times as large a response to cAMP stimulation as prespore cells.

Effect of mutations on the p53 IRES RNA structure Implications for de-regulation of the synthesis of p53 isoforms

Earlier we have demonstrated the presence of internal ribosome entry site (IRES) within tumor suppressor p53 mRNA. Here we have mapped the putative secondary structure of p53-IRES RNA using information from chemical probing and nuclease mapping experiments. Additionally, the secondary structure of the IRES element of the wild-type RNA was compared with cancer-derived silent mutant p53 RNAs. These mutations might result in the conformational alterations of p53-IRES RNAs. The results also indicate decreased IRES activities of the mutants as compared to wild-type RNA. Further, it was observed that some of the cytoplasmic trans-acting factors, critical for enhancing IRES function, were unable to bind mutant RNAs as efficiently as to wild-type. Our results suggest that hnRNP C1/C2 binds to p53-IRES and siRNA mediated partial silencing of hnRNP C1/C2 showed appreciable decrease in IRES function and consequent decrease in the level of the corresponding p53 isoform. Interestingly mutant p53 IRES showed lesser binding with hnRNP C1/C2 protein. Finally, upon doxorubicin treatment, the mutant RNAs were unable to show enhanced p53 synthesis to similar extent compared to wild type. Taken together, these observations suggest that mutations occurring in the p53 IRES might have profound implications for de-regulation of its expression and activity.

Five-level inverter scheme for an open-end winding induction machine with less number of switches

Higher level of inversion is achieved with a less number of switches in the proposed scheme. The scheme proposes a five-level inverter for an open-end winding induction motor which uses only two DC-link rectifiers of voltage rating of Vdc/4, a neutral-point clamped (NPC) three-level inverter and a two-level inverter. Even though the two-level inverter is connected to the high-voltage side, it is always in square-wave operation. Since the two-level inverter is not switching in a pulse width modulated fashion and the magnitude of switching transient is only half compared to the convention three-level NPC inverter, the switching losses and electromagnetic interference is not so high. The scheme is experimentally verified on a 2.5 kW induction machine.

Symmetry-breaking transition in a two-level system coupled to an Ohmic bath: A squeezed-state approach

Displaced squeezed states are proposed as variational ground states for phonons (Bose fields) coupled to two-level systems (spin systems). We have investigated the zero-temperature phase diagram for the localization-delocalization transition of a tunneling particle interacting with an Ohmic heat bath. Our results are compared with known existing approximate treatments. A modified phase diagram using the displaced squeezed state is presented.

The level of sequestered calcium in vegetative amoebae of Dictyostelium discoideum can predict post-aggregative cell fate

When freshly starved amoebae of Dictyostelium discoideum are stained with chlortetracycline (CTC), a cell type-specific fluorescent probe for membrane-associated calcium (Ca2+) the resulting fluorescence distribution falls into two functional classes. Fluorescence-activated cell sorting shows that highly fluorescing amoebae tend to enter the prestalk pathway while those with low fluorescence tend to become prespores. In the light of previous findings, these results indicate that in addition to cell cycle phase at starvation, phenotypic variation in the level of sequestered calcium is an early correlate of cell fate.

Cell versus message level performances in ATM networks

The goal of this paper is to provide some insight into the relations that exist between cell level and message level performance guarantees in the context of ATM networks. Cell level guarantees are typically what the network is capable of providing, while message level guarantees are the ones of interest to users. It is, therefore, important to understand how the two are related, and which factors influence this relation. There are many different performance measures that are of importance, and in this paper we try to touch on the (three) most relevant ones. This includes comparing cell and message loss probabilities, average cell and message delays, and cell and message jitter. Specifically, we show that cell and message loss probabilities can exhibit significant differences, which strongly depend on traffic characteristics such as peak rate and burst size, i.e., for a fixed cell loss probability, the message loss probability can greatly vary when peak rate and burst size change. One reason for this sensitivity, is that message loss depends on what happen to all the cells in a message. For delay and jitter, we also find that peak rate and burst size play a role in determining the relation between cell and message performance. However, this sensitivity is not as acute as with losses since message delay and jitter are typically determined by the performance seen by only one cell, the last cell in a message. In the paper, we provide quantitative examples that illustrate the range of behaviors and identify the impact of different parameters.

Cu 2p core-level photoemission spectrum of Sr2CuO3

We measure the Cu 2p X-ray photoemission spectrum (XPS) of Sr2CuO3 and analyze it by means of exact diagonalization calculations for (CunO3n)(4n-) clusters. In Sr2CuO3, the intensity ratio of the 3d(y) satellite to the 3d(10)(L) under bar main line is 0.35-0.4, which is evidently smaller than that in the other high-T-c related cuprates. We ascribe it as the smaller charge-transfer energy between the Cu 3d and O 2p. The origin of the broad main-line of Sr2CuO3 is also discussed.

Electronic structure of early 3d-transition-metal oxides by analysis of the 2p core-level photoemission spectra

The electronic structures of a wide range of early transition-metal (TM) compounds, including Ti and V oxides with metal valences ranging from 2+ to 5+ and formal d-electron numbers ranging from 0 to 2, have been investigated by a configuration-interaction cluster model analysis of the core-level metal 2p x-ray photoemission spectra (XPS). Inelastic energy-loss backgrounds calculated from experimentally measured electron-energy-loss spectra (EELS) were subtracted from the XPS spectra to remove extrinsic loss features. Parameter values deduced for the charge-transfer energy Delta and the d-d Coulomb repulsion energy U are shown to continue the systematic trends established previously for the late TM compounds, giving support to a charge-transfer mechanism for the satellite structures. The early TM compounds are characterized by a large metal d-ligand p hybridization energy, resulting in strong covalency in these compounds. Values for Delta and U suggest that many early TM compounds should be reclassified as intermediate between the charge-transfer regime and the Mott-Hubbard regime.

Thermodynamics of water entry in hydrophobic channels of carbon nanotubes

Experiments and computer simulations demonstrate that water spontaneously fills the hydrophobic cavity of a carbon nanotube. To gain a quantitative thermodynamic understanding of this phenomenon, we use the recently developed two phase thermodynamics method to compute translational and rotational entropies of confined water molecules inside single-walled carbon nanotubes and show that the increase in energy of a water molecule inside the nanotube is compensated by the gain in its rotational entropy. The confined water is in equilibrium with the bulk water and the Helmholtz free energy per water molecule of confined water is the same as that in the bulk within the accuracy of the simulation results. A comparison of translational and rotational spectra of water molecules confined in carbon nanotubes with that of bulk water shows significant shifts in the positions of the spectral peaks that are directly related to the tube radius. (C) 2011 American Institute of Physics.