C Electron Nuclear Double Resonance Spectroscopy-Guided Molecular Dynamics Computations Reveal the Structure of the Enzyme-Substrate Complex of an Active, -Linked Glycosylated Lipoxygenase.

Lipoxygenase (LOX) enzymes produce important cell-signaling mediators, yet attempts to capture and characterize LOX-substrate complexes by X-ray co-crystallography are commonly unsuccessful, requiring development of alternative structural methods. We previously reported the structure of the complex of soybean lipoxygenase, SLO, with substrate linoleic acid (LA), as visualized through the integration of C/H electron nuclear double resonance (ENDOR) spectroscopy and molecular dynamics (MD) computations. However, this required substitution of the catalytic mononuclear, nonheme iron by the structurally faithful, yet inactive Mn ion as a spin probe.

Water-soluble dinuclear iridium(III) and ruthenium(II) bis-terdentate complexes: photophysics and electrochemiluminescence.

The synthesis, photophysics, and electrochemiluminescence (ECL) of four water-soluble dinuclear Ir(III) and Ru(II) complexes (1-4) terminally-capped by 4'-phenyl-2,2':6',2''-terpyridine (tpy) or 1,3-di(pyrid-2-yl)-4,6-dimethylbenzene (N^C^N) ligands and linked by a 2,7-bis(2,2':6',2''-terpyridyl)fluorene with oligoether chains on C9 are reported. The impact of the tpy or N^C^N ligands and metal centers on the photophysical properties of 1-4 was assessed by spectroscopic methods including UV-vis absorption, emission, and transient absorption, and by time-dependent density functional theory (TDDFT) calculations. These complexes exhibited distinct singlet and triplet excited-state properties upon variation of the terminal-capping terdentate ligands and the metal centers.

Using Spectator Ligands to Enhance Nanocrystal-to-Molecule Electron Transfer.

Semiconductor nanocrystals (NCs) have emerged as promising photocatalysts. However, NCs are often functionalized with complex ligand shells that contain not only charge acceptors but also other "spectator ligands" that control NC solubility and affinity for target reactants. Here, we show that spectator ligands are not passive observers of photoinduced charge transfer but rather play an active role in this process.

Electron-Beam-Induced Molecular Plasmon Excitation and Energy Transfer in Silver Molecular Nanowires.

We investigate (1) electron-beam-induced plasmon absorption spectra of Ag molecular nanowire dimers and (2) electron-beam-induced energy transfer between two nanowires. We employ linear-response time-dependent density functional theory (TDDFT) and real-time TDDFT methods to simulate the electron-beam-induced plasmonic excitations, dynamics, and corresponding electron energy loss spectrum for small models of a single molecular nanowire with four Ag atoms and for two Ag nanowires. An array of different relative orientations of nanowires and of different initial excitation conditions resulting from applying an electron beam at different positions with respect to the Ag nanowires is investigated.

Passivating Nucleobases Bring Charge Transfer Character to Optically Active Transitions in Small Silver Nanoclusters.

DNA-wrapped silver nanoclusters (DNA-AgNCs) are known for their efficient luminescence. However, their emission is highly sensitive to the DNA sequence, the cluster size, and its charge state. To get better insights into photophysics of these hybrid systems, simulations based on density functional theory (DFT) are performed.

Lysosome Targeting Bis-terpyridine Ruthenium(II) Complexes: Photophysical Properties and Photodynamic Therapy.

Three heteroleptic bis-terpyridine ruthenium(II) complexes () [Ru(tpy-R)(tpy-R)] (tpy = 2,2':6',2″-terpyridine, R/R = phenyl, 4-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}phenyl, pyren-1-yl, or 4-phenyl-BODIPY (boron dipyrromethene)) were synthesized and investigated for their potential applications as photosensitizers (PSs) for photodynamic therapy. All complexes displayed broad and intense absorption band in the green spectral regions (450-600 nm), which arose from the spin-allowed charge-transfer transitions mixed with ligand-localized π,π* transitions. All complexes show weak green emission at 513-549 nm and/or even weaker red emission at 646-674 nm at room temperature depending on the excitation wavelength and the solvent used.

Synthesis, Photophysics, and Reverse Saturable Absorption of -Bis-cyclometalated Iridium(III) Complexes (C^N^C)Ir(R-tpy) (tpy = 2,2':6',2″-Terpyridine) with Broadband Excited-State Absorption.

Extending the bandwidth of triplet excited-state absorption in transition-metal complexes is appealing for developing broadband reverse saturable absorbers. Targeting this goal, five bis-terdentate iridium(III) complexes (-) bearing -bis-cyclometalating (C^N^C) and 4'-R-2,2':6',2″-terpyridine (4'-R-tpy) ligands were synthesized. The effects of the structural variation in cyclometalating ligands and substituents at the tpy ligand on the photophysics of these complexes have been systematically explored using spectroscopic methods (i.

A New Class of Homoleptic and Heteroleptic Bis(terpyridine) Iridium(III) Complexes with Strong Photodynamic Therapy Effects.

Six homo- or heteroleptic tricationic Ir(R-tpy)(R-tpy) complexes (-, R/R = Ph, 4'-N(CH)Ph, pyren-1-yl, or 4'-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}Ph, tpy = 2,2';6',2"-terpyridine) were synthesized and tested for photodynamic therapy (PDT) effects. The ground- and excited-state characteristics of these complexes were studied systematically spectroscopic methods and quantum chemistry calculations. All complexes possessed intraligand charge transfer (ILCT) / metal-to-ligand charge transfer (MLCT) dominated transition(s) in their low-energy absorption bands, which red-shifted with the increased electron-releasing strength of the R/R substituent.

Neutral Cyclometalated Iridium(III) Complexes Bearing Substituted N-Heterocyclic Carbene (NHC) Ligands for High-Performance Yellow OLED Application.

The synthesis, crystal structure, and photophysics of a series of neutral cyclometalated iridium(III) complexes bearing substituted N-heterocyclic carbene (NHC) ancillary ligands ((CN)Ir(R-NHC), where CN and NHC refer to the cyclometalating ligand benzo[]quinoline and 1-phenylbenzimidazole, respectively) are reported. The NHC ligands were substituted with electron-withdrawing or -donating groups on C4' of the phenyl ring (R NO (), CN (), H (), OCH (), N(CH) ()) or C5 of the benzimidazole ring (R = NO (), N(CH) ()). The configuration of was confirmed by a single-crystal X-ray diffraction analysis.

Neutral iridium(iii) complexes bearing BODIPY-substituted N-heterocyclic carbene (NHC) ligands: synthesis, photophysics, in vitro theranostic photodynamic therapy, and antimicrobial activity.

The synthesis, photophysics, and photobiological activities of a series of novel neutral heteroleptic cyclometalated iridium(iii) complexes incorporating boron dipyrromethene (BODIPY) substituted N-heterocyclic carbene (NHC) ligands (Ir1-Ir5) are reported. The effect of the substitution position of BODIPY on the NHC ligands, either on C4 of the phenyl ring (Ir1-Ir3) or C5 of the benzimidazole unit (Ir4 and Ir5), and its linker type (single or triple bond) on the photophysical properties was studied. Ir1-Ir5 exhibited BODIPY-localized intense 1IL (intraligand transition)/1MLCT (metal-to-ligand charge transfer) absorption at 530-543 nm and 1,3IL/1,3CT (charge transfer) emission at 582-610 nm.

π-Expansive Heteroleptic Ruthenium(II) Complexes as Reverse Saturable Absorbers and Photosensitizers for Photodynamic Therapy.

Five heteroleptic tris-diimine ruthenium(II) complexes [RuL(N^N)](PF) (where L is 3,8-di(benzothiazolylfluorenyl)-1,10-phenanthroline and N^N is 2,2'-bipyridine (bpy) (1), 1,10-phenanthroline (phen) (2), 1,4,8,9-tetraazatriphenylene (tatp) (3), dipyrido[3,2-a:2',3'-c]phenazine (dppz) (4), or benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (dppn) (5), respectively) were synthesized. The influence of π-conjugation of the ancillary ligands (N^N) on the photophysical properties of the complexes was investigated by spectroscopic methods and simulated by density functional theory (DFT) and time-dependent DFT. Their ground-state absorption spectra were characterized by intense absorption bands below 350 nm (ligand L localized π,π* transitions) and a featureless band centered at ∼410 nm (intraligand charge transfer (ILCT)/π,π* transitions with minor contribution from metal-to-ligand charge transfer (MLCT) transition).