Self-assembled pi-nanotapes as donor scaffolds for selective and thermally gated fluorescence resonance energy transfer (FRET)

Self-assembled nanotapes of a few tailor-made oligo(p-phenylenevinylene)s (OPVs) have been prepared and used as supramolecular donor scaffold to study the fluorescence resonance energy transfer (FRET) to a suitable acceptor. In nonpolar solvents, FRET occurs with nearly 63-81% efficiency, exclusively from the self-assembled OPVs to entrapped Rhodamine B, resulting in the quenching of the donor emission with concomitant formation of the acceptor emission at 625 nm. The efficiency of FRET is considerably influenced by the ability of the OPVs to form the self-assembled aggregates and hence could be controlled by structural variation of the molecules, and polarity of the solvent. Most importantly, FRET could be controlled by temperature as a result of the thermally reversible self-assembly process. The FRET efficiency was significantly enhanced (ca. 90%) in a xerogel film of the OPV1 which is dispersed with relatively less amount of the acceptor (33 mol %), when compared to that of the aggregates in dodecane gel. FRET is not efficient in polar solvents due to weak self-organization of the chromophores. These results indicate that energy transfer occurs exclusively from the self-assembled donor and not directly from the individual donor molecules. The present study illustrates that the self-assembly of chromophores facilitates temperature and solvent controlled FRET within pi-conjugated nanostructures.     

The chemical nature of the 2'-substituent in the pentose-sugar dictates the pseudoaromatic character of the nucleobase (pKa) in DNA/RNA

We here show that the pKa (error limit: 0.01 to 0.03 pKa unit) of a nucleobase in a nucleotide can be modulated by the chemical nature of the 2'-substituent at the sugar moiety. This has been evidenced by the measurement of nucleobase pKa in 47 different model nucleoside 3',5'-bis- and 3'-mono-ethylphosphates. The fact that the electronic character of each of the 2'-substituents (Fig. 1) alters the chemical shift of the H2' sugar proton, and also alters the pKa of the nucleobase in the nucleotides has been evidenced by a correlation plot of pKa of N3 of pyrimidine (T/C/U) or pKa of N7 of 9-guaninyl with the corresponding deltaH2' chemical shifts at the neutral pH, which shows linear correlation with high Pearson's correlation coefficients (R = 0.85-0.97). That this modulation of the pKa of the nucleobase by a 2'-substituent is a through-bond as well as through-space effect has been proven by ab initio determined pKa estimation. Interestingly, experimental pKas of nucleobases from NMR titration and the calculated pKas (by ab initio calculations utilizing closed shell HF 6-31G** basis set) are linearly correlated with R = 0.98. It has also been observed that the difference of ground and protonated/de-protonated HOMO orbital energies (DeltaHOMO, a.u.) for the nucleobases (A/G/C/T/U) are well correlated with their pK(a)s in different 2'-substituted 3',5'-bis-ethylphosphate analogs suggesting that only the orbital energy of HOMO can be successfully used to predict the modulation of the chemical reactivity of the nucleobase by the 2'-substituent. It has also been demonstrated that pKa values of nucleobases in 3',5'-bis-ethylphosphates (Table 1) are well correlated with the change in dipole moment for the respective nucleobases after protonation or de-protonation. This work thus unambiguously shows that alteration of the thermodynamic stability (Tm) of the donor-acceptor complexes [ref. 20], as found with various 2'-modified duplexes in the antisense, siRNA or in triplexes by many workers in the field, is a result of alteration of the pseudoaromatic character of the nucleobases engineered by alteration of the chemical nature of the 2'-substitution.     

Ultrasound frame rate requirements for cardiac elastography: experimental and in vivo results

Cardiac elastography using radiofrequency echo signals can provide improved 2D strain information compared to B-mode image data, provided data are acquired at sufficient frame rates. In this paper, we evaluate ultrasound frame rate requirements for unbiased and robust estimation of tissue displacements and strain. Both tissue-mimicking phantoms under cyclic compressions at rates that mimic the contractions of the heart and in vivo results are presented. Sinusoidal compressions were applied to the phantom at frequencies ranging from 0.5 to 3.5 cycles/sec, with a maximum deformation of 5% of the phantom height. Local displacements and strains were estimated using both a two-step one-dimensional and hybrid two-dimensional cross-correlation method. Accuracy and repeatability of local strains were assessed as a function of the ultrasound frame rate based on signal-to-noise ratio values.The maximum signal-to-noise ratio obtained in a uniformly elastic phantom is 20 dB for both a 1.26 Hz and a 2 Hz compression frequency when the radiofrequency echo acquisition is at least 12 Hz and 20 Hz respectively. However, for compression frequencies of 2.8 Hz and 4 Hz the maximum signal-to-noise ratio obtained is around 16 dB even for a 40 Hz frame rate. Our results indicate that unbiased estimation of displacements and strain require ultrasound frame rates greater than ten times the compression frequency, although a frame rate of about two times the compression frequency is sufficient to estimate the compression frequency imparted to the tissue-mimicking phantom. In vivo results derived from short-axis views of the heart acquired from normal human volunteers also demonstrate this frame rate requirement for elastography.     

Fluorinated Boron Nitride Quantum Dots: A New 0D Material for Energy Conversion and Detection of Cellular Metabolism

Quantum dots encompass a broad spectrum of optical, catalytic, and electrochemical properties bringing in novel applications in catalysis, imaging, displays, and optoelectronics. Herein, the unanticipated broad‐spectrum light absorption and high fluorescence quantum yield in fluorinated boron nitride (FBN) quantum dots are discussed. A heterostructure of FBN quantum dots with a wide‐bandgap semiconductor, titania nanotube arrays, exhibits high photocatalytic activity as evidenced by high external quantum efficiency extending from ultraviolet to green region of the solar spectrum (≈24% at 400 nm). The high activity is confirmed using photoelectrochemical hydrogen evolution experiments. Further, it is demonstrated that high fluorescence quantum yield could be tapped for the detection of glycolytic activity in cancer cells compared to normal cells. This finding could shift the paradigm of molecular detection using quantum dots. The 0D structure and the gap states introduced through fluorination are believed to be responsible for these unprecedented characteristics of boron nitride.     

Late-time tails of fields around Schwarzschild black hole surrounded by quintessence

The evolution of scalar, electromagnetic and gravitational fields around spherically symmetric black hole surrounded by quintessence are studied with special interest on the late-time behavior. In the ring down stage of evolution, we find in the evolution picture that the fields decay more slowly due to the presence of quintessence. As the quintessence parameter $\epsilon $ decreases, the decay of $\ell =0$ mode of scalar field gives up the power-law form of decay and relaxes to a constant residual field at asymptotically late times. The $\ell >0$ modes of scalar, electromagnetic and gravitational fields show a power-law decay for large values of $\epsilon $ , but for smaller values of $\epsilon $ they give way to an exponential decay.     

Inclusion complexes of pantoprazole with β-cyclodextrin and cucurbit[7]uril: experimental and molecular modeling study

The inclusion complexes of the proton pump inhibitor (PPI) pantoprazole sodium (PNZ_Na) with β-cyclodextrin (βCD) and cucurbit[7]uril (CB[7]) have been investigated. Fluorescence spectroscopy and electrospray ionization mass spectrometry (ESI-MS) were used to characterize these complexes. The fluorescence intensity of PNZ_Na was remarkably enhanced by both hosts, indicating the formation of the complexes. Nevertheless, the two hosts are of comparable cavity size their effect on the fluorescence of PNZ_Na was quite different. The ESI-MS data on the other hand confirmed the formation of a 1:1 PNZ_Na: host inclusion complexes for the two hosts. We further utilized molecular dynamics to shed more light on the mechanism of complexation and on the stability of these complexes in aqueous media. The complexes were stabilized over the 20 ns of simulation time mainly via hydrogen bonding interactions in addition to hydrophobic effects and van der Waals interactions. Snapshots collected during the simulations for both complexes have clearly shown that the mode of insertion of PNZ into the two host’s cavities are different which explain the difference in fluorescence enhancement of PNZ obtained in presence of each of these hosts.     

Generalized incomplete Trojan-type designs

Generalized incomplete Trojan-type designs are defined to be row–column designs in which each cell, corresponding to the intersection of row and column, contains more than one treatment and the rows are incomplete. A method of constructing generalized incomplete Trojan-type design has been developed and some properties of this class of designs are discussed.