pH-dependent Si-fluorescein hypochlorous acid fluorescent probe: spirocycle ring-opening and excess hypochlorous acid-induced chlorination.

We report the synthesis and characterization of a fluorescent probe (Hypo-SiF) designed for the detection of hypochlorous acid (HOCl) using a silicon analogue of fluorescein (SiF). The probe is regulated in an "off-on" fashion by a highly selective thioether spirocyclic nonfluorescent structure that opens to form a mixture of fluorescent products in the presence of HOCl. Over a range of pH values, the probe reacts with a stoichiometric amount of HOCl, resulting in a mixture of two pH-dependent fluorescent species, a SiF disulfide product and a SiF sulfonate product. The unique colorimetric properties of the individual SiF fluorophores were utilized to perform simultaneous detection of HOCl and pH. When an excess of HOCl is present, the SiF fluorophores become chlorinated, via an intermediate halohydrin, resulting in a more pH independent and red-shifted fluorophore.

Design and investigation of a series of rhodamine-based fluorescent probes for optical measurements of pH.

A series of structurally similar fluorescent probes (1-4), synthesized from rhodamine B, were designed to optically measure pH. Each probe had a unique "off-on" response as the solution went from basic to acidic. Probes 1-3 exhibited a spirocyclic quenching of the pyronin B fluorophore, whereas probe 4 was quenched by PET from the amine moiety.

Computational studies on response and binding selectivity of fluorescence sensors.

Using a computational strategy based on density functional theory calculations, we successfully designed a fluorescent sensor for detecting Zn(2+) [J. Phys. Chem. B 2006, 110, 22991-22994]. In this work, we report our further studies on the computational design protocol for developing Photoinduced Electron Transfer (PET) fluorescence sensors. This protocol was applied to design a PET fluorescence sensor for Zn(2+) ions, which consists of anthracene as the fluorophore connected to pyridine as the receptor through dimethylethanamine as the linker. B3LYP and time-dependent B3LYP calculations were performed with the basis set 6-31G(d,p), 6-31+G(d,p), 6-311G(d,p), and 6-311+G(d,p). The calculated HOMO and LUMO energies of the fluorophore and receptor using all four basis sets show that the relative energy levels remain unchanged. This indicates that any of these basis sets can be used in calculating the relative molecular orbital (MO) energy levels. Furthermore, the relative MO energies of the independent fluorophore and receptor are not altered when they are linked together, which suggests that one can calculate the MO energies of these components separately and use them as the MO energies of the free sensor. These are promising outcomes for the computational design of sensors, though more case studies are needed to further confirm these conclusions. The binding selectivity studies indicate that the predicted sensor can be used for Zn(2+) even in the presence of the divalent cation, Ca(2+).

Separation of peptides with polyionic nanosponges for MALDI-MS analysis.

A polymer brush consisting of 70% poly(N-isopropylacrylamide) (PNIPAAM) and 30% polymethacrylic acid (PMAA) was synthesized from gold substrates with a "grafting from" AIBN-type free-radical initiator. Fractionation of two peptides, bradykinin and buccalin, was accomplished in less than 120 s by placing a 30 pM (pH approximately 6.2) droplet onto the polymer brush substrate. The eluant containing the anionic buccalin is pipetted away for MALDI analysis while the cationic bradykinin adsorbed to the swollen anionic brush and was subsequently released by adding a droplet of formic acid to the substrate. This caused the brush to collapse and release the bradykinin, much like squeezing a sponge; these nanosponge substrates exhibited very high loading capacity (>2.0 mg/mL) compared to plasma-polymer-modified MALDI substrates. Ellipsometric measurements showed that complementary peptides adsorb rapidly while those of the same charge do not, and MALDI-MS analysis of the two fractions showed separation of both peptides. The adsorption of bradykinin was monitored over time, and 85% of the peptide had been adsorbed to the nanosponge in 1 min from a 0.5 mg/mL aqueous solution.

Computational prediction and experimental evaluation of a photoinduced electron-transfer sensor.

An approach is presented for the design of photoinduced electron-transfer-based sensors. The approach relies on the computational and theoretical prediction of electron-transfer kinetics based on Rehm-Weller and Marcus theories. The approach allows evaluation of the photophysical behavior of a prototype fluorescent probe/sensor prior to the synthesis of the molecule. As a proof of concept, a prototype sensor for divalent metal ions is evaluated computationally, synthesized, and then analyzed spectroscopically for its fluorescence response to zinc. Calculations predicted that the system would show a competition between electron transfer and fluorescence in the free state. In the zinc-bound state, the compound was predicted to be more highly fluorescent, due to the inhibition of electron transfer. Both predictions were confirmed experimentally. A nonzero fluorescence signal was observed in the absence of zinc and an enhancement was observed in the presence of zinc. Specifically, a 56-fold enhancement was observed over a 10-fold increase in zinc concentration.

A hydrogen-bonded heterodimer of 1-(4-hexyloxyphenyl)pyridin-4(1H)-one with 4-cyanobenzoic acid.

The two components of the title heterodimer, C17H21NO2.C8H5NO2, are linked end-to-end via O-H...O(=C) and C-H...O(=C) hydrogen-bond interactions. Additional lateral C-H...O interactions link the dimers in a side-by-side fashion to produce wide infinite molecular ribbons. Adjacent ribbons are interconnected via pi-pi stacking and C-H...pi(arene) interactions. This structure represents the first evidence of robust hydrogen-bond formation between the moieties of pyridin-4(1H)-one and benzoic acid.

Hydrogen-bonded 1:1 adduct of 1,1'-(p-phenylene)dipyridin-4(1H)-one with terephthalic acid.

Cocrystallization of 1,1'-(p-phenylene)dipyridin-4(1H)-one (4,4'-dpy) and terephthalic acid (tpa) affords the hydrogen-bonded 1:1 title complex, C16H12N2O2.C8H6O4. Both molecules are symmetrically disposed about independent symmetry centers. Strong O-H...O hydrogen bonds between tpa carboxyl groups and 4,4'-dpy carbonyl groups produce one-dimensional zigzag infinite chains. Each chain is linked to four surrounding chains via weak C-H...O interactions, resulting in a three-dimensional molecular framework.

N,N',N''-Tris(p-methoxyphenyl)phosphoric triamide.

The title compound, C(21)H(24)N(3)O(4)P, is a self-complementary hydrogen-bond (HB) building unit, with (P=)O as the primary HB acceptor and N-H as the HB donor. Each of the four crystallographically distinct and nearly parallel molecules of the unit cell has a net dipole moment along the P=O bond direction and all of the dipoles are directed in the same general crystallographic direction. Head-to-tail N-H...O=P double-HB strands stack adjacent molecules into one-dimensional infinite polar columns. Each polar column is a 2(1) helix and all columns are essentially parallel, resulting in polar order throughout the entire crystal.

Field control of the surface electroclinic effect in chiral smectic-A liquid crystals.

The surface electroclinic effect, which causes an azimuthal deviation of the layer normal from the surface rubbing direction in cells of chiral smectic- A liquid crystals, can be eliminated (and even reversed) by applying an electric field during cooling from the isotropic phase. The observed dependence of layer orientation on field strength leads to a model in which the surface electroclinic tilt results from an effective surface electric field. The experiements suggest a general method for controlling the azimuthal layer alignment of chiral smectic cells.