Ion-pair reorganization regulates reactivity in photoredox catalysts.

Cyclometalated and polypyridyl complexes of d6 metals are promising photoredox catalysts, using light to drive reactions with high kinetic or thermodynamic barriers via the generation of reactive radical intermediates. However, while tuning of their redox potentials, absorption energy, excited-state lifetime and quantum yield are well-known criteria for modifying activity, other factors could be important. Here we show that dynamic ion-pair reorganization controls the reactivity of a photoredox catalyst, [Ir[dF(CF3)ppy]2(dtbpy)]X. Time-resolved dielectric-loss experiments show how counter-ion identity influences excited-state charge distribution, evincing large differences in both the ground- and excited-state dipole moment depending on whether X is a small associating anion (PF6-) that forms a contact-ion pair versus a large one that either dissociates or forms a solvent-separated pair (BArF4-). These differences correlate with the reactivity of the photocatalyst toward both reductive and oxidative electron transfer, amounting to a 4-fold change in selectivity toward oxidation versus reduction. These results suggest that ion pairing could be an underappreciated factor that modulates reactivity in ionic photoredox catalysts.

Ultrafast exciton dynamics in 2D in-plane hetero-nanostructures: delocalization and charge transfer.

In this article we study the ultrafast dynamics of excitons and charge carriers photogenerated in two-dimensional in-plane heterostructures, namely, CdSe-CdTe nanoplatelets. We combine transient absorption and two-dimensional electronic spectroscopy to study charge transfer and delocalization from a few tens of femtoseconds to several nanoseconds. In contrast with spherical nanocrystals, the relative alignment of the electron and hole states of CdSe and CdTe in thin 2D nanoplatelets does not lead to a type-II heterostructure. Following the excitation in CdSe or CdTe materials, the electron preferentially delocalises instantaneously over the whole heterostructure. In addition, depending on the crown material (CdTe versus CdTeSe), the hole transfers either to trap states or to the crown, within a few hundreds of femtoseconds. We conclude that the photoluminescence band, at lower energy than the CdSe and CdTe first exciton transition, does not result from the recombination of the charge carriers at the charge transfer state but involves localised hole states.

Shared-mode assisted resonant energy transfer in the weak coupling regime.

Recent work has suggested that correlations in the environments of chromophores can lead to a change in the dynamics of excitation transfer in both the coherent and incoherent limits. An example of this effect that is relevant to many single molecule experiments occurs in the standard Forster model for resonant energy transfer (RET). The standard formula for the FRET rate breaks down when the electronic excitations on weakly interacting donor and acceptor couple to the same vibrational modes. The transfer rate can then no longer be factored into donor emission and acceptor absorption lineshapes, but must be recast in terms of a renormalized phonon reorganization energy accounting for the magnitude and sign of the excitation-vibration couplings. In this paper, we derive theoretically how the FRET rate depends on the shared mode structure and coupling, examine the simplified case of Gaussian lineshapes and then provide a quantitative calculation for a system of current interest.

Structure and dynamics of conjugated polymers in liquid crystalline solvents.

A combination of single-molecule spectroscopy and analysis with simulations is used to provide detailed information about the structural and dynamic properties of a fluorescent polymer MEH-PPV (poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene]) immersed in a nematic and smectic solvent. In nematic solvents, single-polymer molecules are oriented strongly along the solvent director, much more so than the solvent molecules, confirming Onsager's old prediction. The diffusion anisotropy parallel and perpendicular to the solvent director, however, is less than two, which is similar to that of a spherical colloid in a nematic solvent. In smectic solvents, there is a second orientation of the dissolved polymer perpendicular to the solvent director, which we hypothesize is caused by the polymer occupying the interlayer volume. The research discussed here emphasizes the importance of organization in complex fluids and suggests that the interplay of order on different length scales could be exploited to fabricate novel nanostructured materials.

Nematic solvation of segmented polymer chains.

We examine the effect of polymer chain segmentation on the recently discovered ability of nematic solvents to elongate and align polymer chain solutes. Coordinated single molecule spectroscopy and beads-on-a-chain simulations are used to study the orientational and conformational order of a series of segmented conjugated polymers, dissolved in the nematic liquid crystal 5CB. The order parameters for alignment and elongation are both observed to decrease with increasing segmentation, reflecting an interplay among conformational entropy, solvation anisotropy, and bending energy of the chain.

Excitation migration along oligophenylenevinylene-based chiral stacks: delocalization effects on transport dynamics.

Atomistic models based on quantum-chemical calculations are combined with time-resolved spectroscopic investigations to explore the migration of electronic excitations along oligophenylenevinylene-based chiral stacks. It is found that the usual Pauli master equation (PME) approach relying on uncoherent transport between individual chromophores underestimates the excitation diffusion dynamics, monitored here by the time decay of the transient polarization anisotropy. A better agreement to experiment is achieved when accounting for excitation delocalization among acceptor molecules, as implemented in a modified version of the PME model. The same models are applied to study light harvesting and trapping in guest-host systems built from oligomers of different lengths.

Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers.

The energy-transfer processes taking place in conjugated polymers are investigated by means of ultrafast spectroscopy and correlated quantum-chemical calculations applied to polyindenofluorenes end-capped with a perylene derivative. Comparison between the time-integrated luminescence and transient absorption spectra measured in solution and in films allows disentangling of the contributions arising from intrachain and from interchain energy-migration phenomena. Intrachain processes dominate in solution where photoexcitation of the polyindenofluorene units induces a rather slow energy transfer to the perylene end moieties. In films, close contacts between chains favors interchain transport of the excited singlet species (from the conjugated bridge of one chain to the perylene unit of a neighboring one); this process is characterized by a 1-order-of-magnitude increase in transfer rate with respect to solution. This description is supported fully by the results of quantum-chemical calculations that go beyond the usual point-dipole model approximation and account for geometric relaxation phenomena in the excited state before energy migration. The calculations indicate a two-step mechanism for intrachain energy transfer with hopping along the conjugated chains as the rate-limiting step; the higher efficiency of the interchain transfer process is mainly due to larger electronic coupling matrix elements between closely lying chains.

Femtosecond dynamics of the forbidden carotenoid S1 state in light-harvesting complexes of purple bacteria observed after two-photon excitation.

Time-resolved excited-state absorption intensities after direct two-photon excitation of the carotenoid S(1) state are reported for light-harvesting complexes of purple bacteria. Direct excitation of the carotenoid S(1) state enables the measurement of subsequent dynamics on a fs time scale without interference from higher excited states, such as the optically allowed S(2) state or the recently discovered dark state situated between S(1) and S(2). The lifetimes of the carotenoid S(1) states in the B800-B850 complex and B800-B820 complex of Rhodopseudomonas acidophila are 7+/-0.5 ps and 6+/-0.5 ps, respectively, and in the light-harvesting complex 2 of Rhodobacter sphaeroides approximately 1.9+/-0.5 ps. These results explain the differences in the carotenoid to bacteriochlorophyll energy transfer efficiency after S(2) excitation. In Rps. acidophila the carotenoid S(1) to bacteriochlorophyll energy transfer is found to be quite inefficient (phi(ET1) <28%) whereas in Rb. sphaeroides this energy transfer is very efficient (phi(ET1) approximately 80%). The results are rationalized by calculations of the ensemble averaged time constants. We find that the Car S(1) --> B800 electronic energy transfer (EET) pathway ( approximately 85%) dominates over Car S(1) --> B850 EET ( approximately 15%) in Rb. sphaeroides, whereas in Rps. acidophila the Car S(1) --> B850 EET ( approximately 60%) is more efficient than the Car S(1) --> B800 EET ( approximately 40%). The individual electronic couplings for the Car S(1) --> BChl energy transfer are estimated to be approximately 5-26 cm(-1). A major contribution to the difference between the energy transfer efficiencies can be explained by different Car S(1) energy gaps in the two species.

Glaucoma filtration surgery: new horizontal mattress closure of conjunctival incision.

We developed a conjunctival wound closure technique with the idea of decreasing the incidence of wound leak following glaucoma filtration surgery. A micropoint 9-0 nylon vascular needle is used as a running mattress suture to close the limbal conjunctiva in routine fornix-based flap trabeculectomy surgery, trabeculectomy surgery with 5-fluorouracil (5-FU), and combined cataract and trabeculectomy surgery. In a series of 52 eyes in 52 patients in which we used this technique, there have been no cases of flat anterior chamber or significant choroidal effusion, complications often occurring secondary to trabeculectomy which require further intervention.

Optical differences in multiple personality disorder. A second look.

The study was designed as a replication of a study reported in this Journal (Miller S [1989] Optical differences in cases of multiple personality disorder. J. Nerv Ment Dis 177:480-486) which found that subjects with multiple personality disorder (MPD) experienced significantly more changes in visual functioning between alter personalities than a control group simulating the disorder. In the present study, data from 20 patients diagnosed with MPD and 20 control subjects role playing MPD were analyzed for statistical and clinical significance. The findings from the present study appear to confirm results from the earlier study that individuals with MPD experience differences in some aspects of visual functioning between alter personalities. The results further confirm that MPD subjects experience more differences across visual measures than control subjects simulating the disorder. However, the findings from the present study are not entirely consistent across the various visual measures or with findings from previous studies.

Simultaneous bilateral conjunctival and orbital lymphoma presenting as a conjunctival lesion.

A 44-year-old man with the diagnosis of a conjunctival lymphoma in the left eye was also found on further evaluation to have a lymphoma in the opposite orbit. The patient had no systemic signs of the disease, and was treated with localized radiation therapy. Although simultaneous presentation of lymphoma affecting the conjunctiva in one eye and the orbit on the opposite side is rare, any patient with an isolated conjunctival lymphoma should have a careful evaluation of the opposite eye and orbit, including an orbital computed tomographic scan to rule out simultaneous involvement.

Clearance of triamcinolone from vitreous.

The clearance of intravitreally injected triamcinolone acetonide was monitored by both indirect ophthalmoscopy and high-performance liquid chromatography (HPLC) and found to be more rapid than previously reported by others. Twenty-four rabbits were intravitreally injected in each eye with 0.4 mg of triamcinolone acetonide. Three rabbits each were sacrificed at intervals ranging from one hour to 46 days. The vitreous was then harvested and processed for HPLC analysis. Triamcinolone and the internal standard prednisolone were identified and quantitated by the use of HPLC, which was found to be both sensitive and specific for the steroids. The half-life as determined by HPLC was 1.6 days, the level at 13 days postinjection was 66 +/- 19 micrograms, and no drug was detectable by HPLC analysis at 21 days in five of six eyes. The intravitreal masses thought to be triamcinolone were clinically observable to an average of 23.3 days. The chromatographically determined clearance rate did not correlate well with clinical impressions based on indirect ophthalmoscopy.

Chemical aspects of radiosensitization. Reaction of sensitizers with radicals produced in the radiolysis of aqueous solutions of nucleic acid components.

The effects of oxidants (sensitizers) in the radiolysis of aqueous solutions of pyrimidine and purine bases have been investigated. Their influence on the nature of the permanent radiolysis products and on the kinetics of disappearance of transient intermediates is reported. Particular attention has been paid to the chemical fates of carbocationic intermediates which can be produced from radical-sensitizer interaction.