Achieving tunable, intense near-infrared absorption in molecular architectures with properties suitable for solar light harvesting and biomedical studies is of fundamental interest. Herein, we report the photophysical, redox, and molecular-orbital characteristics of nine hydroporphyrin dyads and associated benchmark monomers that have been designed and synthesized to attain enhanced light harvesting. Each dyad contains two identical hydroporphyrins (chlorin or bacteriochlorin) connected by a linker (ethynyl or butadiynyl) at the macrocycle β-pyrrole (3- or 13-) or meso (15-) positions. The strong electronic communication between constituent chromophores is indicated by the doubling of prominent absorption features, split redox waves, and paired linear combinations of frontier molecular orbitals. Relative to the benchmarks, the chlorin dyads in toluene show substantial bathochromic shifts of the long-wavelength absorption band (17-31 nm), modestly reduced singlet excited-state lifetimes (τS = 3.6-6.2 ns vs 8.8-12.3 ns), and increased fluorescence quantum yields (Φf = 0.37-0.57 vs 0.34-0.39). The bacteriochlorin dyads in toluene show significant bathochromic shifts (25-57 nm) and modestly reduced τS (1.6-3.4 ns vs 3.5-5.3 ns) and Φf (0.09-0.19 vs 0.17-0.21) values. The τS and Φf values for the bacteriochlorin dyads are reduced substantially (up to ∼20-fold) in benzonitrile. The quenching is due primarily to the increased S1 → S0 internal conversion that is likely induced by increased contribution of charge-resonance configurations to the S1 excited state in the polar medium. The fundamental insights gained into the physicochemical properties of the strongly coupled hydroporphyrin dyads may aid their utilization in solar-energy conversion and photomedicine.

Enzymes in human de novo purine biosynthesis have been demonstrated to form a reversible, transient multienzyme complex, the purinosome, upon purine starvation. However, characterization of purinosomes has been limited to HeLa cells and has heavily relied on qualitative examination of their subcellular localization and reversibility under wide-field fluorescence microscopy. Quantitative approaches, which are particularly compatible with human disease-relevant cell lines, are necessary to explicitly understand the purinosome in live cells. In this work, human breast carcinoma Hs578T cells have been utilized to demonstrate the preferential utilization of the purinosome under purine-depleted conditions. In addition, we have employed a confocal microscopy-based biophysical technique, fluorescence recovery after photobleaching, to characterize kinetic properties of the purinosome in live Hs578T cells. Quantitative characterization of the diffusion coefficients of all de novo purine biosynthetic enzymes reveals the significant reduction of their mobile kinetics upon purinosome formation, the dynamic partitioning of each enzyme into the purinosome, and the existence of three intermediate species in purinosome assembly under purine starvation. We also demonstrate that the diffusion coefficient of the purine salvage enzyme, hypoxanthine phosphoribosyltransferase 1, is not sensitive to purine starvation, indicating exclusion of the salvage pathway from the purinosome. Furthermore, our biophysical characterization of nonmetabolic enzymes clarifies that purinosomes are spatiotemporally different cellular bodies from stress granules and cytoplasmic protein aggregates in both Hs578T and HeLa cells. Collectively, quantitative analyses of the purinosome in Hs578T cells led us to provide novel insights for the dynamic architecture of the purinosome assembly.

Symmetrical, near-infrared absorbing bacteriochlorin dyads exhibit gradual reduction of their fluorescence (intensity and lifetime) and reactive oxygen species photosensitization efficiency (ROS) with increasing solvent dielectric constant ε. For the directly linked dyad, significant reduction is observed even in solvents of moderate ε, while for the dyad containing a 1,4-phenylene linker, reduction is more parallel to an increase in solvent ε. Bacteriochlorin dyads are promising candidates for development of environmentally responsive fluorophores and ROS sensitizers.

A series of a rigid meso-meso directly linked chlorin-chlorin, chlorin-bacteriochlorin, and bacteriochlorin-bacteriochlorin dyads, including free bases as well as Zn(II), Pd(II), and Cu(II) complexes, has been synthesized, and their absorption, emission, singlet oxygen (O) photosensitization, and electronic properties have been examined. Marked bathochromic shifts of the long-wavelength Q absorption band and increase in fluorescence quantum yields in dyads, in comparison to the corresponding monomers, are observed. Nonsymmetrical dyads (except bacteriochlorin-bacteriochlorin) show two distinctive Q bands, corresponding to the absorption of each dyad component. A nearly quantitative S-S energy transfer between hydroporphyrins in dyads, leading to an almost exclusive emission of hydroporphyrin with a lower S energy, has been determined. Several symmetrical and all nonsymmetrical dyads exhibit a significant reduction in fluorescence quantum yields in solvents of high dielectric constants; this is attributed to the photoinduced electron transfer. The complexation of one macrocycle by Cu(II) or Pd(II) enhances intersystem crossing in the adjacent, free base dyad component, which is manifested by a significant reduction in fluorescence and increase in quantum yield of O photosensitization.

Excitonically coupled bacteriochlorin (BC) dimers constitute a primary electron donor (special pair) in bacterial photosynthesis and absorbing units in light-harvesting antenna. However, the exact nature of the excited state of these dyads is still not fully understood. Here, we report a detailed spectroscopic and computational investigation of a series of symmetrical bacteriochlorin dimers, where the bacteriochlorins are connected either directly or by a phenylene bridge of variable length. The excited state of these dyads is quenched in high-dielectric solvents, which we attribute to photoinduced charge transfer. The mixing of charge transfer with the excitonic state causes accelerated (within 41 ps) decay of the excited state for the directly linked dyad, which is reduced by orders of magnitude with each additional phenyl ring separating the bacteriochlorins. These results highlight the origins of the excited-state dynamics in symmetric BC dyads and provide a new model for studying the primary processes in photosynthesis and for the development of artificial, biomimetic systems for solar energy conversion.