Label free phosphate functionalized semiconducting polymer dots for detection of iron(III) and cytochrome c with application to apoptosis imaging.

We report on facile synthesis and characterization of phosphate-functionalized polymer dots (PDs) by doping tributyl phosphate (TBP) in a semiconducting polymer poly[9,9-dioctylfluorenyl-2,7-diyl)-co-1,4-benzo-{2,10-3}-thiadiazole)] (PFBT). Then, the prepared TBP@PFBT PDs were used to develop a very high sensitive probe for detection Fe3+, Cu2+ ions and Cytochrome c based on aggregation induced fluorescence off mechanism. The PDs exhibited a linear dynamic range for Fe3+ from 0.1 to 2 nM with a detection limit of 30 pM and for Cu2+ from 2.0 to 50.0 nM with a detection limit of 0.35 nM. Meanwhile, this probe showed a linear dynamic range for Cyt c from 175 to 1750 pM with a detection limit of 32.7 pM. The TBP@PFBT PDs is a simple, one-step, fast, non-invasive, label-free, and inexpensive probe that is capable of online apoptosis monitoring response to drugs with an ever-present opportunity to contribute in a variety of in-vitro and in-vivo biological applications. We also obtained sharp, specific 2D and 3D imaging results for early stage apoptosis in breast cancer cells. Moreover, this technique possesses the advantage of rapid determination of Fe3+ ion in biological or environmental samples. Importantly, this label-free assay provides short determination time of only a few min, easy operation and very low LOD allowing 100-4000 times increased in sensitivity over previously reported probes, together with high selectivity without need to using biorecognition elements like enzymes, antibodys and/or aptamers. Such excellent features make the TBP@PFBT PDs an excellent probe for successful apoptosis imaging in live cells.

A highly selective semiconducting polymer dots-based "off-on" fluorescent nanoprobe for iron, copper and histidine detection and imaging in living cells.

Semiconducting polymer dots (PDs) hold a great promise as fluorescence nanoprobes, due to their photostability, biocompatibility, and high quantum yield. Herein, the synthesis and characterization of highly fluorescent PDs for selective and sensitive detection of Fe3+,Cu2+, and histidine (His) have been reported. First, carboxyl functionalized poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo-(2,1',3)-thiadiazole)] (PFBT) PDs were synthesized through a nano-precipitation technique, and then they were functionalized by -COOH groups using 9-anthracenecarboxylic acid. The formation of PDs was proved using transmission electron microscopy, dynamic light scattering, and Fourier transform infrared (FTIR) spectroscopy analyses. The PDs exhibited a yellow fluorescence with a peak centered at 540 nm (photo-excited at 460 nm) with a quantum yield of 25%. The fluorescence of PDs significantly quenched in the presence of Cu2+ ion, and then selectively recovered upon addition of His, providing the possibility of constructing a sensitive Cu2+-His off-on fluorescent nanoprobe. The PDs exhibited a linear dynamic range for Cu2+ from 0.1 to 630 µmol L-1 with a limit of detection of 61.7 nmol L-1, and for Fe3+ from 0.1 to 720 µmol L-1 with a limit of detection of 58.1 nmol L-1. In addition, the PDs/Cu2+ probe showed a linear dynamic range for His from 0.1 to 920 µmol L-1 with a limit of detection of 79.6 nmol L-1. Besides, the prepared PDs/Cu2+ probe exhibited a promising potential for selective and sensitive sensing of His in blood serum and for intracellular imaging.

Magnetic resonance tensors in uracil: calculation of 13C, 15N, 17O NMR chemical shifts, 17O and 14N electric field gradients and measurement of 13C and 15N chemical shifts.

The experimental (13)C NMR chemical shift components of uracil in the solid state are reported for the first time (to our knowledge), as well as newer data for the (15)N nuclei. These experimental values are supported by extensive calculated data of the (13)C, (15)N and (17)O chemical shielding and (17)O and (14)N electric field gradient (EFG) tensors. In the crystal, uracil forms a number of strong and weak hydrogen bonds, and the effect of these on the (13)C and (15)N chemical shift tensors is studied. This powerful combination of the structural methods and theoretical calculations gives a very detailed view of the strong and weak hydrogen bond formation by this molecule. Good calculated results for the optimized cluster in most cases (except for the EFG values of the (14)N3 and (17)O4 nuclei) certify the accuracy of our optimized coordinates for the hydrogen nuclei. Our reported RMSD values for the calculated chemical shielding and EFG tensors are smaller than those reported previously. In the optimized cluster the 6-311+G** basis set is the optimal one in the chemical shielding and EFG calculations, except for the EFG calculations of the oxygen nuclei, in which the 6-31+G** basis set is the optimal one. The optimal method for the chemical shielding and EFG calculations of the oxygen and nitrogen nuclei is the PW91PW91 method, while for the chemical shielding calculations of the (13)C nuclei the B3LYP method gives the best results.