Triplet photosensitizers (PSs) are compounds that can be efficiently excited to the triplet excited state which subsequently act as catalysts in photochemical reactions. The name is originally derived from compounds that were used to transfer the triplet energy to other compounds that have only a small intrinsic triplet state yield. Triplet PSs are not only used for triplet energy transfer, but also for photocatalytic organic reactions, photodynamic therapy (PDT), photoinduced hydrogen production from water and triplet-triplet annihilation (TTA) upconversion. A good PS should exhibit strong absorption of the excitation light, a high yield of intersystem crossing (ISC) for efficient production of the triplet state, and a long triplet lifetime to allow for the reaction with a reactant molecule. Most transition metal complexes show efficient ISC, but small molar absorption coefficients in the visible spectral region and short-lived triplet excited states, which make them unsuitable as triplet PSs. One obstacle to the development of new triplet PSs is the difficulty in predicting the ISC of chromophores, especially of organic compounds without any heavy atoms. This review article summarizes some molecular design rationales for triplet PSs, based on the molecular structural factors that facilitate ISC. The design of transition metal complexes with large molar absorption coefficients in the visible spectral region and long-lived triplet excited states is presented. A new method of using a spin converter to construct heavy atom-free organic triplet PSs is discussed, with which ISC becomes predictable, C60 being an example. To enhance the performance of triplet PSs, energy funneling based triplet PSs are proposed, which show broadband absorption in the visible region. Applications of triplet PSs in photocatalytic organic reactions, hydrogen production, triplet-triplet annihilation upconversion and luminescent oxygen sensing are briefly introduced.

Triplet photosensitizers: from molecular design to applications

We reevaluate the absolute fluorescence and phosphorescence quantum yields of standard solutions by using a novel instrument developed for measuring the absolute emission quantum yields of solutions. The instrument consists of an integrating sphere equipped with a monochromatized Xe arc lamp as the light source and a multichannel spectrometer. By using a back-thinned CCD (BT-CCD) as the detector, the sensitivity for spectral detection in both the short and long wavelength regions is greatly improved compared with that of an optical detection system that uses a conventional photodetector. Using this instrument, we reevaluate the absolute fluorescence quantum yields (Φf) of some commonly used fluorescence standard solutions by taking into account the effect of reabsorption/reemission. The value of Φf for 5 × 10−3 M quinine bisulfate in 1 N H2SO4 is measured to be 0.52, which is in good agreement with the value (0.508) obtained by Melhuish by using a modified Vavilov method. In contrast, the value of Φf for 1.0 × 10−5 M quinine bisulfate in 1 N H2SO4, which is one of the most commonly used standards in quantum yield measurements based on the relative method, is measured to be 0.60. This value is significantly larger than Melhuish’s value (0.546), which was estimated by extrapolating the value of Φf for 5 × 10−3 M quinine bisulfate solution to infinite dilution using the self-quenching constant. The fluorescence quantum yield of 9,10-diphenylanthracene in cyclohexane is measured to be 0.97. This system can also be used to determine the phosphorescence quantum yields (Φp) of metal complexes that emit phosphorescence in the near-infrared region: the values of Φp for [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) are estimated to be 0.063 in water and 0.095 in acetonitrile under deaerated conditions at 298 K, while that in aerated water, which is frequently used as a luminescent reference in biological studies, is reevaluated to be 0.040.

Reevaluation of absolute luminescence quantum yields of standard solutions using a spectrometer with an integrating sphere and a back-thinned CCD detector.

Chemical Science Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352; Department of Chemistry, ShelbyHall, University of Alabama, Box 870336, Tuscaloosa, Alabama 35487-0336; Notre Dame Radiation Laboratory, University of Notre Dame,Notre Dame, Indiana 46556; Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 0520-8107; Argonne NationalLaboratory, 9700 South Cass Avenue, Argonne, Illinois 60439; Department of Computer Science and Department of Physics, 2710 University Drive,Washington State University, Richland, Washington 99352-1671; Lawrence Berkeley National Laboratory, 1 Cyclotron Road Mailstop 1-0472,Berkeley, California 94720; Department of Chemistry and Biochemistry, University of Texas at Austin, 1 University Station A5300,Austin, Texas 78712; Office of Basic Energy Sciences, U.S. Department of Energy, SC-141/Germantown Building, 1000 Independence Avenue,S.W., Washington, D.C. 20585-1290; Department of Physics and Engineering Physics, Stevens Institute of Technology, Castle Point on Hudson,Hoboken, New Jersey 07030; Department of Chemistry, Johns Hopkins University, 34th and Charles Streets, Baltimore, Maryland 21218;Department of Chemistry, University of Southern California, Los Angeles, California 90089-1062; Department of Chemistry, The Ohio StateUniversity, 100 West 18th Avenue, Columbus, Ohio 43210-1185; Department of Chemistry, Columbia University, Box 3107, Havemeyer Hall,New York, New York 10027; Department of Chemistry, University of Pittsburgh, Parkman Avenue and University Drive,Pittsburgh, Pennsylvania 15260; Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000; Department of Physics andAstronomy, Rutgers, The State University of New Jersey, 136 Frelinghuysen Road, Piscataway, New Jersey 08854-8019; Department of Chemistry,516 Rowland Hall, University of California, Irvine, Irvine, California 92697-2025; Stanford Synchrotron Radiation Laboratory, Stanford LinearAccelerator Center, 2575 Sand Hill Road, Mail Stop 69, Menlo Park, California 94025; School of Chemistry and Biochemistry, Georgia Institute ofTechnology, 770 State Street, Atlanta, Georgia 30332-0400; Geology Department, University of California, Davis, One Shields Avenue,Davis, California 95616-8605; Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue,Cambridge, Massachusetts 02139-4307; Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084Received July 23, 2004

http://casey.brown.edu/chemistry/research/LSWang/publications/194.pdf

Role of water in electron-initiated processes and radical chemistry: issues and scientific advances.

Transition Metal Alkane Complexes

Optical theranostic nanoagents that seamlessly and synergistically integrate light-generated signals with photothermal or photodynamic therapy can provide opportunities for cost-effective precision medicine, while the potential for clinical translation requires them to have good biocompatibility and high imaging/therapy performance. We herein report an intraparticle molecular orbital engineering approach to simultaneously enhance photoacoustic brightness and photothermal therapy efficacy of semiconducting polymer nanoparticles (SPNs) for in vivo imaging and treatment of cancer. The theranostic SPNs have a binary optical component nanostructure, wherein a near-infrared absorbing semiconducting polymer and an ultrasmall carbon dot (fullerene) interact with each other to induce photoinduced electron transfer upon light irradiation. Such an intraparticle optoelectronic interaction augments heat generation and consequently enhances the photoacoustic signal and maximum photothermal temperature of SPNs by 2.6- a...

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Intraparticle Molecular Orbital Engineering of Semiconducting Polymer Nanoparticles as Amplified Theranostics for In Vivo Photoacoustic Imaging and Photothermal Therapy

George E. Heibel

Papers

Time-resolved photothermal and photoacoustic methods applied to photoinduced processes in solution

Time‐Resolved Photothermal and Photoacoustic Methods Applied to Photoinduced Processes in Solution