Biomedical subjects

Guillermo C Bazan

Publications and source records attributed to Guillermo C Bazan.

At least 19 recordsLinked to original sources

PubMed2007

Rapid proton-coupled electron-transfer of hydroquinone through phenylenevinylene bridges.

We describe the synthesis of two oligo(phenylene vinylene)s (OPVs) with a hydroquinone moiety and a thiol anchor group: 4-(2',5'-dihydroxystyryl)benzyl thioacetate and 4-[4'-(2' ',5' '-dihydroxystyryl)styryl]benzyl thioacetate. Monolayers on gold of these molecules were examined by electrochemical techniques to determine the electron transfer kinetics of the hydroquinone functionality (H2Q) through these delocalized tethers ("molecular wires") as a function of pH. Between pH 4 and 9, rate constants were ca. 100-fold faster than for the same H2Q functionality confined to the surface via alkane tethers. Also, in this same pH range rate constants were independent of the length of the OPV bridge. These new electroactive molecules in which the hydroquinone functionality is wired to the gold surface by means of OPV tethers should be useful platforms for constructing bioelectronic devices such as biosensors, biofuel cells, and biophotovoltaic cells with a fast response time.

Chemistry, Physical↗

PubMed2006

Control of interchain contacts, solid-state fluorescence quantum yield, and charge transport of cationic conjugated polyelectrolytes by choice of anion.

Simple procedures are provided for exchanging charge-compensating ions in conjugated polyelectrolytes by progressive dilution of the original species and for determining the degree of ion exchange by using X-ray photoelectron spectroscopy. By using these methods, the bromide ions in poly[(9,9-bis(6'-N,N,N-trimethylammoniumbromide)hexyl)fluorene-co-alt-4,7-(2,1,3-benzothiadiazole)]were exchanged with BF4-, CF3SO3-, PF6-, BPh4-, and B(3,5-(CF3)2C6H3)4- (BArF4-). Absorption, photoluminescence (PL), and PL quantum yields (Phi) were measured in different solvents and in solid films cast from methanol. Examination of the resulting trends, together with the spectral bandshapes in different solvents, suggests that increasing the counteranion (CA) size decreases interchain contacts and aggregation and leads to a substantial increase of Phi in the bulk. Size analysis of polymers containing Br- and BArF4- in water by dynamic light scattering techniques indicates suppression of aggregation by BArF4-. Nanoscale current-voltage measurements of films using conducting atomic force microscopy show that hole mobilities and, more significantly, charge injection barriers are CA dependent. These results show that it is possible to significantly modify the optoelectronic properties of conjugated polyelectrolytes by choosing different counterions. A parent conjugated backbone can thus be fine-tuned for specific applications.

Anions↗

PubMed2006

Aggregation-mediated optical properties of pH-responsive anionic conjugated polyelectrolytes.

Conjugated polyelectrolyte copolymers containing 2,1,3-benzothiadiazole- (BT) and oligo(ethylene oxide)-substituted fluorene and phenylene units have been designed and synthesized. The phenylene pendent groups also have carboxylic acid functionalities, which allow probing the effect of pH on optical properties. The BT content in the backbone can be regulated at the synthesis stage. Dynamic light scattering studies show that polymers aggregate in water at low pH. Increased interchain contacts give rise to a lowering of the photoluminescence (PL) efficiency via self-quenching when the BT units are absent and increased levels of FRET from the phenylene-fluorene segments to BT. Furthermore, the PL efficiency of BT increases in the aggregated structures. Examination of solvent effects indicates that the increased BT efficiencies are likely due to decreased contact with water. The changes in PL efficiencies are reversible, showing that the aggregates are dynamic and not kinetically constrained.

Anions↗

PubMed2006

Comparison of the signaling and stability of electrochemical DNA sensors fabricated from 6- or 11-carbon self-assembled monolayers.

We have characterized the solution-phase and dry storage stability of electrochemical E-DNA sensors fabricated using mixed self-assembled monolayers (SAMs) composed of 6- or 11-carbon (C6 and C11, respectively) alpha,omega-thiol alcohols and the analogous C6- or C11-thiol-terminated stem-loop DNA probe. We find that the solution-phase and dry storage stability of C6-based E-DNA sensors are limited and poorly reproducible. The use of stabilizing agents bovine serum albumin plus either glucose or trehalose significantly improves the dry storage shelf life of such sensors: when using these preservatives, we observe only 7-9% sensor degradation after 1 month of storage in air at room temperature. In comparison, the stability of C11-based E-DNA sensors is significantly greater than that of the C6-based sensors; we observe only minor (5-8%) loss of signal upon storing these sensors for a week under ambient solution conditions or for more than a month in air in the presence of preservatives. Moreover, whereas the electron-transfer rate through C11 SAMs is slower than that observed for C6 SAMs, it is rapid enough to support good sensor performance. It thus appears that C11 SAMs provide a reasonable compromise between electron-transfer efficiency and sensor stability and are well suited for use in electronic DNA-sensing applications.

Alcohols↗

PubMed2006

Control of cationic conjugated polymer performance in light emitting diodes by choice of counterion.

Counterion exchange in cationic conjugated polyelectrolytes provides for a straightforward method to modulate the performance of these materials as the electron transport (injection) layer (ETL) in organic light emitting diodes. The bromide counterions of [(9,9-bis(6'-N,N,N-trimethylammonium)-hexyl)fluorene]bromide (PF-Br) can be easily replaced with trifluoromethylsulfonate (PF-CF3SO3), tetrakis(imidazolyl)borate (PF-BIm4) or tetrakis(3,5-trifluoromethylphenyl)borate (PF-BArF4) by a procedure that involves precipitation and washing. The performance of LEDs using MEH-PPV as the emissive layer, Al as the cathode, and the conjugated polyelectrolytes as the ETL varies in the order: PF-BIm4 > PF-CF3SO3 > PF-Br > PF-BArF4. In the case of PF-BIm4, the luminous efficiencies of the devices are similar to those of devices using Ba as the cathode. Thus, by properly choosing the counterion one can use higher work function metals that are more stable than lower work function metals without a substantial barrier to electron injection.

Journal Article↗

PubMed2006

Silver nanocrystal-modified silicon nanowires as substrates for surface-enhanced Raman and hyper-Raman scattering.

Metal catalyzed, CVD-grown silicon nanowires decorated by chemical assembly of closely spaced Ag nanocrystals were modified with the well-known "silver mirror" reaction and investigated as substrates for surface-enhanced Raman (SERS) and hyper-Raman (SEHRS) spectroscopy. Four chromophores were examined: Rhodamine 6G, crystal violet, a cyanine dye, and a cationic donor-acceptor substituted stilbene. After soaking the substrates overnight in 10(-4) M aqueous chromophore solutions, all four chromophores gave good-quality SERS spectra in < or =60 s using <1 microW of 458-nm cw laser power, and SEHRS spectra are obtained in < or =120 s using <1 mW of mode-locked 916-nm laser power. Results from this substrate are compared with those on colloidal silver nanoparticles deposited as a film, as well as surfaces grown by the silver mirror reaction.

Microscopy, Electron, Scanning↗

PubMed2006

Single-molecule charge-transport measurements that reveal technique-dependent perturbations.

We compare scanning tunneling microscopy (STM) imaging with single-molecule conductive atomic force microscopy (C-AFM) measurements by probing a series of structurally related thiol-terminated oligo(phenylenevinylene)s (OPVs) designed to have unique charge-transport signatures. When one or two methylene spacers are inserted between the thiol points of attachment and the OPV core, a systematic reduction in the imaged molecular transconductance and the current transmitted through a metal-molecule-metal junction containing the molecule is observed, indicating good agreement between STM and C-AFM measurements. However, a structure where the OPV backbone is interrupted by a [2.2]paracyclophane core has a low molecular transconductance, as determined from STM images, and a high measured single-molecule conductance. This apparent disconnect can be understood by comparing the calculated molecular orbital topology of the OPV with one thiol bound to a gold surface (the geometry in the STM experiment) with the topology of the molecule with both thiol termini bound to gold (relevant to C-AFM). In the former case, a single contact splits low-lying molecular orbitals into two discrete fragments, and in the latter case, molecular orbitals that span the entire molecule are observed. Although the difference in observed conductance between the two different measurements is resolved, the overall set of observations highlights the importance of using combined techniques to better characterize charge-transport properties relevant to molecular electronics.

Journal Article↗

PubMed2006

Solvent effects on resonant first hyperpolarizabilities and Raman and hyper-Raman spectra of DANS and a water-soluble analog.

The two-photon-resonant first hyperpolarizabilities associated with hyper-Rayleigh and hyper-Raman scattering are reported for 4-dimethylamino-4-nitrostilbene in 1,4-dioxane, dichloromethane, acetonitrile, and methanol, and for an ionic analog, 4-N,N-bis(6-(N,N,N-trimethylammonium)-hexyl)amino-4-nitrostilbene dibromide in methanol and water. Resonance Raman and hyper-Raman excitation profiles are also measured and modeled. The resonance Raman and hyper-Raman spectra show very similar relative intensities which do not vary much as the excitation frequency is tuned across the lowest-energy strong linear absorption band, suggesting that a single resonant electronic state dominates the one- and two-photon absorptions in this region. The absorption, resonance Raman, and hyper-Raman profiles can be simulated reasonably well with a common set of parameters. The peak resonant (absolute value of beta)2, measured by hyper-Rayleigh scattering, varies by about 50% over the range of solvents examined and shows a weak correlation with the linear absorption maximum, with the redder-absorbing systems exhibiting larger peak hyperpolarizabilities. The experimental hyper-Rayleigh intensities are higher than those calculated, possibly reflecting contributions from nonresonant electronic states.

Journal Article↗

PubMed2006

PNA/dsDNA complexes: site specific binding and dsDNA biosensor applications.

The ability of peptide nucleic acids (PNA) to form specific higher-order (i.e., three- and four-stranded) complexes with DNA makes it an ideal structural probe for designing strand-specific dsDNA biosensors. Higher-order complexes are formed between a dye-labeled charge-neutral PNA probe and complementary dsDNA. Addition of a light-harvesting cationic conjugated polymer (CCP) yields supramolecular structures held together by electrostatic forces that incorporate the CCP and the dye-labeled PNA/DNA complexes. Optimization of optical properties allows for excitation of the CCP and subsequent fluorescence resonance energy transfer (FRET) to the PNA-bound dye. In the case of noncomplementary dsDNA, complexation between the probe and target does not occur, and dye emission is weak. The binding between PNA and noncomplementary and complementary dsDNA was examined by several methods. Gel electrophoresis confirms specificity of binding and the formation of higher-order complexes. Nano-electrospray mass spectrometry gives insight into the stoichiometric composition, including PNA/DNA, PNA(2)/DNA, PNA/DNA(2), and PNA(2)/DNA(2) complexes. Finally, structural characteristics and binding-site specificity were examined using ion mobility mass spectrometry in conjunction with molecular dynamics. These results give possible conformations for each of the higher-order complexes formed and show exclusive binding of PNA to the complementary stretch of DNA for all PNA/DNA complexes. Overall, the capability and specificity of binding indicates that the CCP/PNA assay is a feasible detection method for dsDNA and eliminates the need for thermal denaturing steps typically required for DNA hybridization probe assays.

Biosensing Techniques↗

PubMed2006

Quadruplex-to-duplex transition of G-rich oligonucleotides probed by cationic water-soluble conjugated polyelectrolytes.

G-quartet DNA converts to duplex form in the presence of its complementary strand. This conformational change can be detected in real time by a homogeneous assay method based on the signal amplification of conjugated polyelectrolytes and the specific interaction of intercalating dyes with double-stranded DNA (dsDNA). The probe solution contains a cationic, conjugated polymer (CCP), G-quadruplex labeled with a fluorescein at the 5'-terminus (G-quadruplex-Fl), and ethidium bromide (EB). The addition of a complementary target results in the transition from G-quadruplex to duplex (dsDNA-Fl) and EB intercalation within the duplex structure. Excitation of the CCP leads to energy transfer from CCP to dsDNA-Fl (FRET-1) and then energy transfer from dsDNA-Fl to EB (FRET-2). Increasing the number of mismatched bases discourages dsDNA formation, which is detected in the assay.

Cations↗

PubMed2006

Optical coherence and theoretical study of the excitation dynamics of a highly symmetric cyclophane-linked oligophenylenevinylene dimer.

Optoelectronic properties of a polyphenylenevinylene-based oligomer and its paracylophane-linked dimer are studied using a variety of experimental and theoretical techniques. Despite the symmetrical structure and redshifted absorption of the dimer versus the monomer, an exciton picture is not the most appropriate. Electronic structure calculations establish changes in charge density upon optical excitation and show localized excitations that cannot be accounted for by a simple Frenkel exciton model. Visible frequency pump-probe anisotropy measurements suggest that the dimer should be considered as a three-level system with a fast, approximately 130 fs, internal conversion from the higher to lower energy excited electronic state. Signatures of nuclear relaxation processes are compared for electric field-resolved transient grating and two-dimensional photon echo spectra. These measurements reveal that nuclear relaxation occurs on similar time scales for the monomer and dimer. The connection between the spectral phase of four-wave mixing signals and the time dependent width of a nuclear wave packet is discussed. Semiempirical electronic structure and metropolis Monte Carlo calculations show that the dominant line broadening mechanisms for the monomer and dimer are associated with inter-ring torsional coordinates. Together, the theoretical calculations and electric field-resolved four-wave mixing experiments suggest that while the structure of dimer is more rigid than that of monomer, the difference in their rigidities is not sufficient to slow down excited state relaxation of dimer with respect to the monomer.

Journal Article↗

PubMed2006

Simulation of single molecule inelastic electron tunneling signals in paraphenylene-vinylene oligomers and distyrylbenzene[2.2]paracyclophanes.

Inelastic resonances in the electron tunneling spectra of several conjugated molecules are simulated using the nonequilibrium Greens function formalism. The vibrational modes that strongly couple to the electronic current are different from the infrared and Raman active modes. Spatially resolved inelastic electron tunneling (IET) intensities are predicted. The simulated IET intensities for a large distyrylbenzene paracyclophane molecule are in qualitative agreement with recent experimental results.

Journal Article↗

PubMed2006

Red electrophosphorescence from a soluble binaphthol derivative as host and iridium complex as guest.

The investigation of the optical properties, carrier injection, and transport into a soluble small molecule, 6,6'-dicarbazolyl-2,2'-dihexyloxy-1,1'-binaphthol (BA), was reported. The results demonstrated that BA is a blue-emitting molecule, which can be used as a host for the fabrication of electrophosphorescent light-emitting diodes (LEDs). The single-layer electrophosphorescent LEDs fabricated from toluene solution containing BA with tris[2,5-bis-2'-(9',9'-dihexylfluorene)pyridine-kappa(2)NC(3)(')]iridium(III) [Ir(HFP)(3)] emitted red light from Ir(HFP)(3) triplet emission. The results from photoluminescence (PL) and electroluminescence (EL) demonstrated that the dominated operational mechanism in EL was charge trapping rather than Förster transfer, which was the dominated mechanism in PL. The single-layer OLEDs with 1wt % of Ir(HFP)(3) have a luminance (L) of 1000 cd/m(2) at 22 V and a luminous efficiency (LE) of 0.88 cd/A at 11 mA/cm(2). Double-layer electrophosphorescent LEDs fabricated by casting the emitting layer from a solution of BA blended with Ir(HFP)(3) and subsequently thermally depositing tris(8-hydroxyquinoline) aluminum (Alq(3)) film as an electron injection and transport layer yielded L = 1830 cd/m(2) at 30 V and LE = 2.47 cd/A at 18 mA/cm(2). These results demonstrated that electrophosphorescent LEDs can be fabricated from BA via solution processing and that L and LE can be enhanced by changing the device architecture with the goal of better balancing the electron and hole currents.

Journal Article↗

PubMed2006

Optimization of the molecular orbital energies of conjugated polymers for optical amplification of fluorescent sensors.

Cationic water-soluble poly(fluorene-co-phenylene)s with electron withdrawing or donating substituents on the conjugated backbone were designed and synthesized. Fluorescence resonance energy transfer (FRET) experiments between these conjugated polymers and dye-labeled single-stranded DNA (ssDNA-C*) reveal the importance of matching donor and acceptor orbital energy levels to improve the sensitization of C* emission. Quenching of polymer fluorescence with ssDNA-C* and differences in C* emission suggest involvement of photoinduced charge transfer (PCT) as an energy wasting mechanism. The HOMO and LUMO energy levels of the conjugated polymers and C serve as a preliminary basis to understand the competition between FRET and PCT. Dilution of C in polymer/ssDNA-C complexes by addition of ssDNA yields insight into C*...C self-quenching. Under optimized conditions, where there is no probe self-quenching and minimum PCT, efficient signal amplification is demonstrated despite poor spectral overlap between polymer and C.

Biosensing Techniques↗

PubMed2005

Matrix-induced intensity fluctuations in the fluorescence from single oligo(phenylenevinylene) molecules.

Single molecule spectroscopy on oligo(phenylenevinylene) (OPV) chromophores shows that the fluorescence intermittency strongly correlates to the rigidity of the environment surrounding the molecules. For OPV single molecules, environmental rigidity inhibits twisting about the vinyl linkages, the molecular motion associated with the observed "off" (nonabsorbing) state. By increasing the rigidity of a single molecule's environment, we can tune its room temperature fluorescence from rapid, sub-millisecond "blinking" fluctuations (fluid polymer environment) to completely "on" with no blinking observed (molecules adsorbed to a rigid bare glass substrate). The difference in fluorescence intermittency from environment to environment is immediately apparent and explicit in single molecule intensity trajectories under cw (continuous wave) excitation, demonstrating the sensitivity of these chromophores to their surroundings and emphasizing the importance of morphological control in real-world applications involving phenylenevinylene-based materials.

Journal Article↗

PubMed2005

Solvent effects on the two-photon absorption of distyrylbenzene chromophores.

A series of organic- and water-soluble distyrylbenzene-based two-photon absorption (TPA) fluorophores containing dialkylamino donor groups at the termini was designed, synthesized, and characterized. The central core was systematically substituted to modulate intramolecular charge transfer (ICT). These molecules allow an examination of solvent effects on the TPA cross section (delta) and on the TPA action cross section. In toluene, the delta values follow the order of ICT strength. The effect of solvent on delta is nonmonotonic: maximum delta was measured in an intermediate polarity solvent (THF) and was lowest in water. We failed to find a correlation between the observed solvent effect and previous theoretical predictions. Hydrogen bonding to the donor groups and aggregation of the optical units in water, which are not included in calculational analysis, may be responsible for the discrepancies between experimental results and theory.

Absorption↗

PubMed2005

Chelate bis(imino)pyridine cobalt complexes: synthesis, reduction, and evidence for the generation of ethene polymerization catalysts by Li+ cation activation.

Treatment of the bis(iminobenzyl)pyridine chelate Schiff-base ligand 8 (ligPh) with FeCl2 or CoCl2 yielded the corresponding (ligPh)MCl2 complexes 9 (Fe) and 10 (Co). The reaction of 10 with methyllithium or "butadiene-magnesium" resulted in reduction to give the corresponding (ligPh)Co(I)Cl product 11. Similarly, the bis(aryliminoethyl)pyridine ligand (ligMe) was reacted with CoCl2 to yield (ligMe)CoCl2 (12). Reduction to (ligMe)CoCl (13) was effected by treatment with "butadiene-magnesium". Complex 13 reacted with Li[B(C6F5)4] in toluene followed by treatment with pyridine to yield [(ligMe)Co+-pyridine] (15). The reaction of the Co(II) complexes 10 or 12 with ca. 3 molar equiv of methyllithium gave the cobalt(I) complexes 16 and 17, respectively. Treatment of the (ligMe)CoCH3 (17) with Li[B(C6F5)4] gave a low activity ethene polymerization catalyst. Likewise, complex 16 produced polyethylene (activity = 33 g(PE) mmol(cat)(-1) h(-1) bar(-1) at room temperature) upon treatment with a stoichiometric amount of Li[B(C6F5)4]. A third ligand (lig(OMe)) was synthesized featuring methoxy groups in the ligand backbone (22). Coordination to FeCl2 and CoCl2 yielded the desired compounds 23 and 24. Reaction with MeLi gave (ligOMe)CoMe (25/26). Treatment of 25/26 with excess B(C6F5)3 gave the eta6-arene cation complex 27, where one Co-N linkage was cleaved. Activation of 25/26 with Li[B(C6F5)4] again gave a catalytically active species.

Catalysis↗

PubMed2005

Two-photon absorption in aqueous micellar solutions.

Addition of the surfactant sodium dodecyl sulfate at concentrations above the critical micelle concentration increases the fluorescence quantum yield and the two-photon absorption cross-section of charged [2.2]paracyclophane chromophores containing pairs of D-pi-D chromophores. The resulting spectra in the micellar solutions are very similar to those obtained for neutral isostructural analogues in toluene. The measured etadelta values are 1300 GM for 1C and 1920 GM for 2C, which are comparable or larger to those in toluene. These results highlight possible misleading interpretation of two-photon-induced emission for evaluating the concentration of labeled substrates used in two-photon microscopy and provide guidelines for designing molecular structures with optimized two-photon action cross-sections in water.

Acetates↗