Reconciliation of Differences in Apparent Diffusion Coefficients Measured for Self-Exchange Electron Transfer between Molecules Anchored to Mesoporous Titanium Dioxide Thin Films.

Redox-active sites present at large concentrations as part of a solid support or dissolved as molecules in fluid solutions undergo reversible self-exchange electron-transfer reactions. These processes can be monitored using a variety of techniques. Chronoamperometry and cyclic voltammetry are common techniques used to interrogate this behavior for molecules bound to mesoporous thin films of wide-bandgap semiconductors and insulators. In order to use these techniques to obtain accurate values for apparent diffusion coefficients, which are proxies for rate constants for self-exchange electron transfer, it is imperative to take into consideration nonidealities in redox titrations, parasitic currents, and ohmic resistances. Using spectroelectrochemical measurements taken concurrently with measurements of chronoamperometry data, we show that the spectroscopic data is not confounded from effects of parasitic currents or electroinactive dyes. However, we show that the thickness of the thin film over the region that is optically probed by the measurements must be known. When each of these considerations is included in data analyses, calculated apparent diffusion coefficients are, within error, independent of the method used to obtain the data. These considerations help reconcile variations in apparent diffusion coefficients measured using different techniques that have been reported over the past several decades and allow correct analyses to be performed in the future, independent of the method used to obtain the data.

A pathogenesis-related 10 protein catalyzes the final step in thebaine biosynthesis.

The ultimate step in the formation of thebaine, a pentacyclic opiate alkaloid readily converted to the narcotic analgesics codeine and morphine in the opium poppy, has long been presumed to be a spontaneous reaction. We have detected and purified a novel enzyme from opium poppy latex that is capable of the efficient formation of thebaine from (7S)-salutaridinol 7-O-acetate at the expense of labile hydroxylated byproducts, which are preferentially produced by spontaneous allylic elimination. Remarkably, thebaine synthase (THS), a member of the pathogenesis-related 10 protein (PR10) superfamily, is encoded within a novel gene cluster in the opium poppy genome that also includes genes encoding the four biosynthetic enzymes immediately upstream. THS is a missing component that is crucial to the development of fermentation-based opiate production and dramatically improves thebaine yield in engineered yeast.

Direct observation of sequential oxidations of a titania-bound molecular proxy catalyst generated through illumination of molecular sensitizers.

Natural photosynthesis uses the energy in sunlight to oxidize or reduce reaction centres multiple times, therefore preparing each reaction centre for a multiple-electron-transfer reaction that will ultimately generate stable reaction products. This process relies on multiple chromophores per reaction centre to quickly generate the active state of the reaction centre and to outcompete deleterious charge recombination. Using a similar design principle, we report spectroscopic evidence for the generation of a twice-oxidized TiO2-bound molecular proxy catalyst after low-intensity visible-light excitation of co-anchored molecular Ru(II)-polypyridyl dyes. Electron transfer from an excited dye to TiO2 generated a Ru(III) state that subsequently and repeatedly reacted with neighbouring Ru(II) dyes via self-exchange electron transfer to ultimately oxidize a distant co-anchored proxy catalyst before charge recombination. The largest yield for twice-oxidized proxy catalysts occurred when they were present at low coverage, suggesting that large dye/electrocatalyst ratios are also desired in dye-sensitized photoelectrochemical cells.

Design, Synthesis, and Self-Assembly of Polymers with Tailored Graft Distributions.

Grafting density and graft distribution impact the chain dimensions and physical properties of polymers. However, achieving precise control over these structural parameters presents long-standing synthetic challenges. In this report, we introduce a versatile strategy to synthesize polymers with tailored architectures via grafting-through ring-opening metathesis polymerization (ROMP). One-pot copolymerization of an ω-norbornenyl macromonomer and a discrete norbornenyl comonomer (diluent) provides opportunities to control the backbone sequence and therefore the side chain distribution. Toward sequence control, the homopolymerization kinetics of 23 diluents were studied, representing diverse variations in the stereochemistry, anchor groups, and substituents. These modifications tuned the homopolymerization rate constants over 2 orders of magnitude (0.36 M-1 s-1 < khomo < 82 M-1 s-1). Rate trends were identified and elucidated by complementary mechanistic and density functional theory (DFT) studies. Building on this foundation, complex architectures were achieved through copolymerizations of selected diluents with a poly(d,l-lactide) (PLA), polydimethylsiloxane (PDMS), or polystyrene (PS) macromonomer. The cross-propagation rate constants were obtained by nonlinear least-squares fitting of the instantaneous comonomer concentrations according to the Mayo-Lewis terminal model. In-depth kinetic analyses indicate a wide range of accessible macromonomer/diluent reactivity ratios (0.08 < r1/r2 < 20), corresponding to blocky, gradient, or random backbone sequences. We further demonstrated the versatility of this copolymerization approach by synthesizing AB graft diblock polymers with tapered, uniform, and inverse-tapered molecular "shapes." Small-angle X-ray scattering analysis of the self-assembled structures illustrates effects of the graft distribution on the domain spacing and backbone conformation. Collectively, the insights provided herein into the ROMP mechanism, monomer design, and homo- and copolymerization rate trends offer a general strategy for the design and synthesis of graft polymers with arbitrary architectures. Controlled copolymerization therefore expands the parameter space for molecular and materials design.

Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush.

Grafting density is an important structural parameter that exerts significant influences over the physical properties of architecturally complex polymers. In this report, the physical consequences of varying the grafting density (z) were studied in the context of block polymer self-assembly. Well-defined block polymers spanning the linear, comb, and bottlebrush regimes (0 ≤ z ≤ 1) were prepared via grafting-through ring-opening-metathesis polymerization. ω-Norbornenyl poly(d,l-lactide) and polystyrene macromonomers were copolymerized with discrete comonomers in different feed ratios, enabling precise control over both the grafting density and molecular weight. Small-angle X-ray scattering experiments demonstrate that these graft block polymers self-assemble into long-range-ordered lamellar structures. For 17 series of block polymers with variable z, the scaling of the lamellar period with the total backbone degree of polymerization (d* ∼ Nbbα) was studied. The scaling exponent α monotonically decreases with decreasing z and exhibits an apparent transition at z ≈ 0.2, suggesting significant changes in the chain conformations. Comparison of two block polymer systems, one that is strongly segregated for all z (System I) and one that experiences weak segregation at low z (System II), indicates that the observed trends are primarily caused by the polymer architectures, not segregation effects. A model is proposed in which the characteristic ratio (C∞), a proxy for the backbone stiffness, scales with Nbb as a function of the grafting density: C∞ ∼ Nbbf(z). The scaling behavior disclosed herein provides valuable insights into conformational changes with grafting density, thus introducing opportunities for block polymer and material design.

CO2 Reduction Selective for C≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives.

Electrocatalytic CO2 reduction to generate multicarbon products is of interest for applications in artificial photosynthetic schemes. This is a particularly attractive goal for CO2 reduction by copper electrodes, where a broad range of hydrocarbon products can be generated but where selectivity for C-C coupled products relative to CH4 and H2 remains an impediment. Herein we report a simple yet highly selective catalytic system for CO2 reduction to C≥2 hydrocarbons on a polycrystalline Cu electrode in bicarbonate aqueous solution that uses N-substituted pyridinium additives. Selectivities of 70-80% for C2 and C3 products with a hydrocarbon ratio of C≥2/CH4 significantly greater than 100 have been observed with several additives. 13C-labeling studies verify CO2 to be the sole carbon source in the C≥2 hydrocarbons produced. Upon electroreduction, the N-substituted pyridinium additives lead to film deposition on the Cu electrode, identified in one case as the reductive coupling product of N-arylpyridinium. Product selectivity can also be tuned from C≥2 species to H2 (∼90%) while suppressing methane with certain N-heterocyclic additives.

Control of Grafting Density and Distribution in Graft Polymers by Living Ring-Opening Metathesis Copolymerization.

Control over polymer sequence and architecture is crucial to both understanding structure-property relationships and designing functional materials. In pursuit of these goals, we developed a new synthetic approach that enables facile manipulation of the density and distribution of grafts in polymers via living ring-opening metathesis polymerization (ROMP). Discrete endo,exo-norbornenyl dialkylesters (dimethyl DME, diethyl DEE, di-n-butyl DBE) were strategically designed to copolymerize with a norbornene-functionalized polystyrene (PS), polylactide (PLA), or polydimethylsiloxane (PDMS) macromonomer mediated by the third-generation metathesis catalyst (G3). The small-molecule diesters act as diluents that increase the average distance between grafted side chains, generating polymers with variable grafting density. The grafting density (number of side chains/number of norbornene backbone repeats) could be straightforwardly controlled by the macromonomer/diluent feed ratio. To gain insight into the copolymer sequence and architecture, self-propagation and cross-propagation rate constants were determined according to a terminal copolymerization model. These kinetic analyses suggest that copolymerizing a macromonomer/diluent pair with evenly matched self-propagation rate constants favors randomly distributed side chains. As the disparity between macromonomer and diluent homopolymerization rates increases, the reactivity ratios depart from unity, leading to an increase in gradient tendency. To demonstrate the effectiveness of our method, an array of monodisperse polymers (PLAx-ran-DME1-x)n bearing variable grafting densities (x = 1.0, 0.75, 0.5, 0.25) and total backbone degrees of polymerization (n = 167, 133, 100, 67, 33) were synthesized. The approach disclosed in this work therefore constitutes a powerful strategy for the synthesis of polymers spanning the linear-to-bottlebrush regimes with controlled grafting density and side chain distribution, molecular attributes that dictate micro- and macroscopic properties.

Ratiometric temperature imaging using environment-insensitive luminescence of Mn-doped core-shell nanocrystals.

We report a ratiometric temperature imaging method based on Mn luminescence from Mn-doped CdS-ZnS nanocrystals (NCs) with controlled doping location, which is designed to exhibit strong temperature dependence of the spectral lineshape while being insensitive to the surrounding chemical environment. Ratiometric thermometry on the Mn luminescence spectrum was performed by using Mn-doped CdS-ZnS core-shell NCs that have a large local lattice strain on the Mn site, which results in the enhanced temperature dependence of the bandwidth and peak position. The Mn luminescence spectral lineshape is highly robust with respect to the change in the polarity, phase and pH of the surrounding medium and aggregation of the NCs, showing great potential in temperature imaging under chemically heterogeneous environment. The temperature sensitivity (ΔIR/IR = 0.5%/K at 293 K, IR = intensity ratio at two different wavelengths) is highly linear in a wide range of temperatures from cryogenic to above-ambient temperatures. We demonstrate the surface temperature imaging of a cryo-cooling device showing a temperature variation of >200 K by imaging the luminescence of the NC film formed by simple spin coating, taking advantage of the environment-insensitive luminescence.

Effect of surfactant and solvent on spin-lattice relaxation dynamics of magnetic nanocrystals.

The effect of varying the surfactant and solvent medium on the dynamics of spin-lattice relaxation in photoexcited Fe3O4 nanocrystals has been investigated by measuring the time-dependent magnetization employing pump-probe transient Faraday rotation technique. The variation of the surfactants having surface-binding functional groups modified not only the static magnetization but also the dynamics of the recovery of the magnetization occurring via spin-lattice relaxation in the photoexcited Fe3O4 nanocrystals. The variation of the polarity and size of the solvent molecules can also influence the spin-lattice relaxation dynamics. However, the effect is limited to the nanocrystals having sufficiently permeable surfactant layer, where the small solvent molecules (e.g., water) can access the surface and dynamically modify the ligand field on the surface.

Doping location-dependent energy transfer dynamics in Mn-doped CdS/ZnS nanocrystals.

Dynamics of energy transfer and charge carrier localization in Mn-doped CdS/ZnS core/shell nanocrystals correlated with doping location and concentration are studied via transient absorption measurement of exciton relaxation dynamics. The strong dependence of exciton-Mn energy transfer rate on doping location was directly resolved in the transient bleach recovery and electron intraband absorption data by using layer-by-layer synthesized Mn-doped nanocrystals. With 1.2 nm decrease in doping radius in the ZnS shell, energy transfer rate increases by 6 fold. We identified that hole trapping is the major competing process that inhibits the energy transfer in Mn-doped CdS/ZnS nanocrystals. From the branching ratio of the energy transfer and hole trapping, combined with luminescence quantum yield measurement, we also obtained doping location-dependent radiative relaxation quantum yield of Mn(2+) ions that is as high as 0.95.

Energy transfer cassettes in silica nanoparticles target intracellular organelles.

Lipophilic energy transfer cassettes like 1 and 2 are more conveniently synthesized than the corresponding hydrophilic compounds, but they are not easily used in aqueous media. To overcome the latter issue, cassettes 1 and 2 were separately encapsulated in silica nanoparticles (ca. 22 nm) which freely disperse in aqueous media. Photophysical properties of the encapsulated dyes 1-SiO(2) and 2-SiO(2) were recorded. The nanoparticles 1-SiO(2) permeated into Clone 9 rat liver cells and targeted only the ER. A high degree of energy transfer was observed in this organelle such that most of the light fluoresced from the acceptor part, i.e. the particles appeared red. Silica nanoparticles 2-SiO(2) also permeated into Clone 9 rat liver cells and they targeted mitochondria but were also observed in endocytic vesicles (lysosomes or endosomes). In these organelles they fluoresced red and red/green respectively. Thus the cargo inside the nanoparticles influences where they localize in cells, and the environment of the nanoparticles in the cells changes the fluorescent properties of the encapsulated dyes. Neither of these findings were anticipated given that silica nanoparticles of this type are generally considered to be non-porous.

Effective shielding of triplet energy transfer to conjugated polymer by its dense side chains from phosphor dopant for highly efficient electrophosphorescence.

To examine the quenching of a triplet exciton by low triplet energy (E(T)) polymer hosts with different chain configurations for high E(T) phosphor guests, the quenching rate constant measurements were carried out and analyzed by the standard Stern-Volmer equation. We found that an effective shielding of triplet energy transfer from a high E(T) phosphor guest to a low E(T) polymer host is possible upon introducing dense side chains to the polymer to block direct contact from the guest such that the possibility of Dexter energy transfer between them is reduced to a minimum. Together with energy level matching to allow charge trapping on the guest, high device efficiency can be achieved. The extent of shielding for the systems of phenylene-based conjugated structures from iridium complexes follows the sequence di-substituted (octoxyl chain) in the para position (dC8OPPP) is greater than monosubstituted (mC8OPPP) and the PPPs with longer side chains are much higher than a phenylene tetramer (P4) with two short methyl groups. Further, capping the dialkoxyl-susbstituents with a carbazole (Cz) moiety (CzPPP) provides enhanced extent of shielding. Excellent device efficiency of 30 cd/A (8.25%) for a green electrophosphorescent device can be achieved with CzPPP as a host, which is higher than that of dC8OPPP as host (15 cd/A). The efficiency is higher than those of high E(T) conjugated polymers, poly(3,6-carbazole) derivatives, as hosts (23 cd/A). This observation suggests a new route for molecular design of electroluminescent polymers as a host for a phosphorescent dopant.