Metal-enhanced fluorescence of dye-doped silica nano particles.

Recent advancements in metal-enhanced fluorescence (MEF) suggest that it can be a promising tool for detecting molecules at very low concentrations when a fluorophore is fixed near the surface of metal nanoparticles. We report a simple method for aggregating multiple gold nanoparticles (GNPs) on Rhodamine B (RhB)-doped silica nanoparticles (SiNPs) utilizing dithiocarbamate (DTC) chemistry to produce MEF in solution. Dye was covalently incorporated into the growing silica framework via co-condensation of a 3-aminopropyltriethoxysilane (APTES) coupled RhB precursor using the Stöber method. Electron microscopy imaging revealed that these mainly non-spherical particles were relatively large (80 nm on average) and not well defined. Spherical core-shell particles were prepared by physisorbing a layer of RhB around a small spherical silica particle (13 nm) before condensing an outer layer of silica onto the surface. The core-shell method produced nanospheres (~30 nm) that were well defined and monodispersed. Both dye-doped SiNPs were functionalized with pendant amines that readily reacted with carbon disulfide (CS2) under basic conditions to produce DTC ligands that have exhibited a high affinity for gold surfaces. GNPs were produced via citrate reduction method and the resulting 13 nm gold nanospheres were then recoated with an ether-terminated alkanethiol to provide stability in ethanol. Fluorescent enhancement was observed when excess GNPs were added to DTC coated dye-doped SiNPs to form nanoparticle aggregates. Optimization of this system gave a fluorescence brightness enhancement of over 200 fold. Samples that gave fluorescence enhancement were characterized through Transmission Emission Micrograph (TEM) to reveal a pattern of multiple aggregation of GNPs on the dye-doped SiNPs.

Fluorescence-on response via CB7 binding to viologen-dye pseudorotaxanes.

Fluorescence-on sensors typically rely on disrupting photoinduced electron transfer quenching of the excited state through binding the electron donor. To provide a more general fluorescence-on signaling unit, a quencher-fluorophore dyad has been developed in which quenching by electron transfer to a tethered viologen acceptor can be disrupted through complexation of the viologen by cucurbit[7]uril (CB7). Dyads of benzyl viologen-rhodamine B or a BODIPY fluorophore gave upon CB7 complexation 14- and 30-fold fluorescence enhancement, respectively.

Kinetics of formation of the host-guest complex of a viologen with cucurbit[7]uril.

Host-guest complexation between the dicationic viologen 1-tri(ethylene glycol)-1'-methyl-m-xylyl-4,4'-bipyridinium and cucurbit[7]uril (CB7) was studied at pH = 4.5 in water. The stability constants of the mono- and bis-CB7 adducts were determined at 25 °C by UV-vis spectroscopy. Stopped-flow kinetic experiments were performed to measure the formation and dissociation rate constants of the monoadduct: k(1) = (6.01 ± 0.03) × 10(6) M(-1)s(-1) and k(-1) = 52.7 ± 0.4 s(-1), respectively. Possible mechanisms of complexation are discussed in view of the kinetic results.

Cucurbit[7]uril disrupts aggregate formation between rhodamine B dyes covalently attached to glass substrates.

Dye aggregation is detrimental to the performance of high optical density dye-doped photonic materials. To overcome this challenge, the ability of cucurbit[7]uril (CB7) as a molecular host to disrupt aggregate formation on glass substrates was examined. Rhodamine B was covalently attached to glass slides by initially coating the surface with azidohexylsiloxane followed by copper-catalyzed "click" triazole formation with rhodamine B propargyl ester. The absorption and emission spectra of rhodamine B coated slides in water indicated diverse heterogeneous properties as surface dye density varied. Fluorescence quenching due to dye aggregation was evident at high surface dye density. Addition of aqueous cucurbit[7]uril (CB7) to the surface-tethered dyes perturbed the spectra to reveal a considerable reduction in heterogeneity, which suggested that the presence of a surface in close proximity does not significantly impair CB7's ability to complex with tethered rhodamine B.

Molecularly ordered decanethiolate self-assembled monolayers on Au(111) from in situ cleaved decanethioacetate: an NMR and STM study of the efficacy of reagents for thioacetate cleavage.

The cleavage of decanethioacetate (C10SAc) has been studied by (1)H nuclear magnetic resonance (NMR) spectroscopy and scanning tunneling microscopy (STM) imaging of in situ prepared decanethiolate self-assembled monolayers (SAMs) on Au(111). Solutions of C10SAc (46 mM) and previously reported cleavage reagents (typically 58 mM) in CD(3)OD were monitored at 20 degrees C by NMR spectroscopy. Cleavage by ammonium hydroxide, propylamine, or hydrochloric acid was not complete within 48 h; cleavage by potassium carbonate was complete within 24 h and that by potassium hydroxide or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) within 2 h. Similar cleavage rates were observed for phenylthioacetate. The degree of molecular ordering determined by STM imaging increased with increasing extent of in situ cleavage by these same reagents (2.5 mM C10SAc and 2.5 mM reagent in ethanol for 1 h, then 16 h immersion of Au/mica). Less effective cleavage reagents did not cleave the C10SAc sufficiently to decanethiol (C10SH) and gave mostly disordered SAMs. In contrast, KOH or DBU completely cleaved the C10SAc to C10SH and led to well-ordered SAMs composed of (square root(3) x square root(3))R30 degrees domains that are indistinguishable from SAMs grown from C10SH. Monolayer formation from thioacetates in the absence of cleavage agents is likely due to thiol or disulfide impurity in the thioacetates. Eliminating disulfide by using Bu(3)P as a sacrificial reductant also helped to produce good molecular order in the SAM. The methods presented here allow routine growth of molecularly ordered alkanethiolate SAMs from thioacetates using reagents of ordinary purity under ambient, benchtop conditions.

Disrupting aggregation of tethered rhodamine B dyads through inclusion in cucurbit[7]uril.

Hexano- and dodecano-tethered diesters of rhodamine B were prepared. The absorption and fluorescence spectra of these flexibly tethered dyads were compared with those of the rhodamine 3B ethyl ester. Increased J- and H-type dimer formation and decreased fluorescence emission were observed for the tethered dyads. Complexation of the cationic chromophoric units in cucurbit[7]uril (CB7) hosts decreased H-dimer aggregation, especially for the dodecano-tethered dyad. The monomeric dye and both dye dyads exhibited enhanced fluorescence upon addition of CB7.

Translational isomerizations in [2]catenanes with unsymmetrically substituted resorcinol-based tethers.

The translational isomerizations of nine [2]catenanes (2-10) containing an electron-rich dibenzo-34-crown-10 ether (BPP34C10) interlocked with rings containing an unsymmetric 4-substituted (chloro, ethyl, or hexyl) resorcinol-based tether linking two electron-deficient dipyridyl groups have been studied by variable temperature (VT) 1H NMR spectroscopy. The second symmetric tether between the dipyridyl groups was a large 5-(4-tert-butylphenyl)-1,3-xylyl (catenanes 2-4), a narrower 1,3-xylyl (catenanes 5-7), or a narrow 1,4-xylyl (catenanes 8-10) group. The presence of the unsymmetrically placed substituent on the resorcinol tether substantially affected the binding energy of the BPP34C10 ring when pi-stacked over either of the dipyridyl groups; the equilibrium constant between the bistable states was found to range from 1.5 to 3.5. The origin of these energy differences is postulated to stem from an unsymmetric twisting of the resorcinol tether to minimize interaction between the 4-substituent and the ethoxy group at the 3-position. The activation barriers for passage over the 4-substituted resorcinol-based tether were 12.5, 13, and 15 kcal/mol for the chloro, ethyl, and hexyl substituents, respectively.

Conformational interconversions in [2]catenanes containing a wide rigid bis(p-benzyl)methyl spacer.

The conformational interconversions of four [2]catenanes (1-4) containing a dibenzo-34-crown-10 ether (BPP34C10) interlocked with rings containing two 4,4'-dipyridiniums tethered by 1,3-bis(ethyloxy)phenyl and bis(p-benzyl)methyl spacers have been studied by VT 1H NMR spectroscopy. Symmetrically placed blocking groups on thickened tethers enabled either pathway for circumrotation of the BPP34C10 between isoenergetic sites to be blocked. On the basis of chemical shifts of the BPP34C10, its internal p-hydroquinone forms pi-pi-stacking interactions with only one 4,4'-dipyridinium ring at a time. The activation barrier for migration along either open tether was approximately 11.5 kcal/mol. This study demonstrates an ability to select the pathway for conformational interconversions in these [2]catenanes containing the rigid bis(p-benzyl)methyl tether and the lowering the barrier for interconversion through destabilization of the ground state structures.

Path selection for conformational interconversions in [2]catenanes.

[strucure: see text]The conformational interconversions of several [2]catenanes containing a dibenzo-34-crown-10 ether (BPP34C10) interlocked with rings containing two 4,4'-dipyridyls tethered by different aryl spacers have been studied. Blocking groups on the tethers enabled the two pathways for circumrotation of the BPP34C10 to be open or blocked. The activation barrier for migration along the open tethers varied from 11 to 13 kcal/mol. This study demonstrates an ability to select the pathway for conformational interconversions in [2]catenanes.