Study of Fluorescence Quenching Ability of Graphene Oxide with a Layer of Rigid and Tunable Silica Spacer.

The fluorescence quenching property of graphene oxide (GO) has been newly demonstrated and applied for fluorescence imaging and biosensing. In this work, a new nanostructure was designed for effectively studying the quenching ability of GO. The key element in this design is the fabrication of a layer of rigid and thickness adjustable silica spacer for manipulating the distance between the GO and fluorophores. First, a silica core modified with organic dye molecules was prepared, followed by the formation of a silica shell with a tunable thickness. Afterward, the GO was wrapped around silica nanoparticles based on the electrostatic interaction between the negatively charged GO and positively charged silica. The quenching efficiency of GO to different dye molecules was studied at various spacer thicknesses and varying concentrations of GO. Fluorescence lifetime of fluorophores was measured to determine the quenching mechanism. We found that the quenching efficiency of GO was still around 30% when the distance between dyes and GO was increased to more than 30 nm, which indicated the long-distance quenching ability of GO and confirmed the previous theoretical calculation. The quenching mechanisms were proposed schematically based on our experimental results. We expected that the proposed nanostructure could act as a feasible model for studying GO quenching property and shed light on designing GO-based fluorescence sensing systems.

Synthesis and Electron Spin Relaxation of Tetracarboxylate Pyrroline Nitroxides.

We report the design, synthesis, and electron spin relaxation properties of hydrophilic tetracarboxylate ester pyrroline nitroxides 1 and 2, which serve as models in the search for new spin labels for DEER distance measurement at room temperature. The nitroxides are designed to have the methyl groups further away from the N-O spin site to decrease the inequivalent couplings of the unpaired electron to the methyl protons that shorten Tm at T > 70 K in currently used labels. The key step in the synthesis of 1 and 2 is the reaction of the dianion of pyrrole-1,2,5-tricarboxylic acid tert-butyl ester dimethyl ester with electrophiles such as methyl chloroformate and methyl bromoacetate. Structures of 1 and 2 are confirmed by X-ray crystallography. Studies of electron spin relaxation rates in rigid trehalose/sucrose matrices reveal approximately temperature independent values of 1/Tm for 1 and 2 up to about 160 K and modest temperature dependence up to 295 K, demonstrating that increasing the distance between the nitroxide moiety and methyl groups is effective in lengthening Tm at T > 70 K.

Electron spin relaxation of a boron-containing heterocyclic radical.

Preparation of the stable boron-containing heterocyclic phenanthrenedione radical, (C6F5)2B(O2C14H8), by frustrated Lewis pair chemistry has been reported recently. Electron paramagnetic resonance measurements of this radical were made at X-band in toluene:dichloromethane (9:1) from 10 to 293K, in toluene from 180 to 293K and at Q-band at 80K. In well-deoxygenated 0.1mM toluene solution at room temperature hyperfine splittings from 11B, four pairs of 1H, and 5 pairs of 19F contribute to an EPR spectrum with many resolved lines. Observed hyperfine couplings were assigned based on DFT calculations and account for all of the fluorines and protons in the molecule. Rigid lattice g values are gx=2.0053, gy=2.0044, and gz=2.0028. Near the melting point of the solvent 1/Tm is enhanced due to motional averaging of g and A anisotropy. Increasing motion above the melting point enhances 1/T1 due to contributions from tumbling-dependent processes. The overall temperature dependence of 1/T1 from 10 to 293K was modeled with the sum of contributions of a process that is linear in T, a Raman process, spin rotation, and modulation of g anisotropy by molecular tumbling. The EPR measurements are consistent with the description of this compound as a substituted aromatic radical, with relatively small spin density on the boron.