Disentangling Hot Carrier Decay and the Nature of Low-n to High-n Transfer Processes in Quasi-Two-Dimensional Layered Perovskites.

Quasi-two-dimensional (2D) metal halide perovskites (MHPs) are promising photovoltaic (PV) materials because of their impressive optical and optoelectronic properties and improved stability compared to their 3D counterparts. The presence of domains with varying numbers of inorganic layers between the organic spacers (n-phases), each with different bandgaps, makes the photoinduced carrier dynamics in films of these materials complex and intriguing. Existing interpretations of the ultrafast femto- or picosecond spectroscopy data have been inconsistent, most of them focusing either on exciton/charge transfer from low-n to high-n phases or on hot carrier cooling, but not combined. Here, we present a comprehensive study of the carrier dynamics in the Dion-Jacobson type (PDMA)(MA)(n-1)PbnI(3n+1) (PDMA = 1,4-phenylenedimethylammonium, MA = methylammonium) perovskite, stoichiometrically prepared as ⟨n⟩ = 5. Within the film, a coexistence of various n-phases is observed instead of solely the n = 5 phase, resulting in an interesting energy landscape for the motion of excitons and charge carriers. We disentangle hot carrier cooling from exciton transfer between low-n and high-n phases using ultrafast time-resolved photoluminescence and transient absorption spectroscopy. Photophysical modeling by target analysis shows that carrier cooling occurring on a subpicosecond time scale is followed by exciton transfer from low-n into high-n phases in ca. 35 ps when the film is excited by 532 or 490 nm light. Carriers in the high-n phase are much longer lived and decay in a ns time window. Overall, our results provide a comprehensive understanding of the photophysics of this material, which helps to optimize quasi-2D MHP materials for a new generation of PV devices.

Nanoscale Thermometry of Plasmonic Structures via Raman Shifts in Copper Phthalocyanine.

Temperature measurements at the nanoscale are vital for the application of plasmonic structures in medical photothermal therapy and materials science but very challenging to realize in practice. In this work, we exploit a combination of surface-enhanced Raman spectroscopy together with the characteristic temperature dependence of the Raman peak maxima observed in ß-phase copper phthalocyanine (ß-CuPc) to measure the surface temperature of plasmonic gold nanoparticles under laser irradiation. We begin by measuring the temperature-dependent Raman shifts of the three most prominent modes of ß-CuPc films coated on an array of Au nanodisks over a temperature range of 100-500 K. We then use these calibration curves to determine the temperature of an array of Au nanodisks irradiated with varying laser powers. The extracted temperatures agree quantitatively with the ones obtained via numerical modeling of electromagnetic and thermodynamic properties of the irradiated array. Thin films of ß-CuPc display low extinction coefficients in the blue-green region of the visible spectrum as well as exceptional thermal stability, allowing a wide temperature range of operation of our Raman thermometer, with minimal optical distortion of the underlying structures. Thanks to the strong thermal response of the Raman shifts in ß-CuPc, our work opens the opportunity to investigate photothermal effects at the nanoscale in real time.

Pulsed Photothermal Heterogeneous Catalysis.

Anthropogenic climate change urgently calls for the greening and intensification of the chemical industry. Most chemical reactors make use of catalysts to increase their conversion yields, but their operation at steady-state temperatures limits their rate, selectivity, and energy efficiency. Here, we show how to break such a steady-state paradigm using ultrashort light pulses and photothermal nanoparticle arrays to modulate the temperature of catalytic sites at timescales typical of chemical processes. Using heat dissipation and time-dependent microkinetic modeling for a number of catalytic landscapes, we numerically demonstrate that pulsed photothermal catalysis can result in a favorable, dynamic mode of operation with higher energy efficiency, higher catalyst activity than for any steady-state temperature, reactor operation at room temperature, resilience against catalyst poisons, and access to adsorbed reagent distributions that are normally out of reach. Our work identifies the key experimental parameters controlling reaction rates in pulsed heterogeneous catalysis and provides specific recommendations to explore its potential in real experiments, paving the way to a more energy-efficient and process-intensive operation of catalytic reactors.

Ultrafast Thermal Imprinting of Plasmonic Hotspots.

Plasmonic photochemistry is driven by a rich collection of near-field, hot charge carrier, energy transfer, and thermal effects, most often accomplished by continuous wave illumination. Heat generation is usually considered undesirable, because noble metal nanoparticles heat up isotropically, losing the extreme energy confinement of the optical resonance. Here it is demonstrated through optical and heat-transfer modelling that the judicious choice of nanoreactor geometry and material enables the direct thermal imprint of plasmonic optical absorption hotspots onto the lattice with high fidelity. Transition metal nitrides (TMNs, e.g., TiN/HfN) embody the ideal material requirements, where ultrafast electron-phonon coupling prevents fast electronic heat dissipation and low thermal conductivity prolongs the heat confinement. The extreme energy confinement leads to unprecedented peak temperatures and internal heat gradients (>10 K nm-1 ) that cannot be achieved using noble metals or any current heating method. TMN nanoreactors consequently yield up to ten thousand times more product in pulsed photothermal chemical conversion compared with noble metals (Ag, Au, Cu). These findings open up a completely unexplored realm of nano-photochemistry, where adjacent reaction centers experience substantially different temperatures for hundreds of picoseconds, long enough for bond breaking to occur.

Using Hot Electrons and Hot Holes for Simultaneous Cocatalyst Deposition on Plasmonic Nanostructures.

Hot electrons generated in metal nanoparticles can drive chemical reactions and selectively deposit cocatalyst materials on the plasmonic hotspots, the areas where the decay of plasmons takes place and the hot electrons are created. While hot electrons have been extensively used for nanomaterial formation, the utilization of hot holes for simultaneous cocatalyst deposition has not yet been explored. Herein, we demonstrate that hot holes can drive an oxidation reaction for the deposition of the manganese oxide (MnOx) cocatalyst on different plasmonic gold (Au) nanostructures on a thin titanium dioxide (TiO2) layer, excited at their surface plasmon resonance. An 80% correlation between the hot-hole deposition sites and the simulated plasmonic hotspot location is showed when considering the typical hot-hole diffusion length. Simultaneous deposition of more than one cocatalyst is also achieved on one of the investigated plasmonic systems (Au plasmonic nanoislands) through the hot-hole oxidation of a manganese salt and the hot-electron reduction of a platinum precursor in the same solution. These results add more flexibility to the use of hot carriers and open up the way for the design of complex photocatalytic nanostructures.

Tunable plasmonic HfN nanoparticles and arrays.

We present the fabrication of tunable plasmonic hafnium nitride (HfN) nanoparticles. HfN is a metallic refractory material with the potential of supporting plasmon resonances in the visible range, similar to silver and gold, but with the additional benefits of high melting point, chemical stability, and mechanical hardness. However, the preparation of HfN nanoparticles and the experimental demonstration of their plasmonic potential are still in their infancy. Here, high quality HfN thin films were fabricated, for which ellipsometry shows their plasmonic potential. From these thin films, nanorods and nanotriangles were milled using a focused ion beam and the plasmon resonances were identified using cathodoluminescence mapping. As an alternative fabrication strategy, an optimized electron-beam lithography procedure was used to prepare arrays of HfN nanoparticles, which also exhibited clear surface plasmon resonances. These results pave the way to further explore HfN nanoparticles in plasmonically-powered applications where materials robustness is essential.

Self-Optimized Catalysts: Hot-Electron Driven Photosynthesis of Catalytic Photocathodes.

Photogenerated hot electrons from plasmonic nanostructures are very promising for photocatalysis, mostly due to their potential for enhanced chemical selectivity. Here, we present a self-optimized fabrication method of plasmonic photocathodes using hot-electron chemistry, for enhanced photocatalytic efficiencies. Plasmonic Au/TiO2 nanoislands are excited at their surface plasmon resonance to generate hot electrons in an aqueous bath containing a platinum (cocatalyst) precursor. Hot electrons drive the deposition of Pt cocatalyst nanoparticles, without any nanoparticle functionalization and negligible applied bias, close to the hotspots of the plasmonic nanoislands. The presence of TiO2 is crucial for achieving higher chemical reaction rates. The Au/TiO2/Pt photocathodes synthesized using hot-electron chemistry show a photocatalytic activity of up to 2 times higher than that of a control made with random electrodeposited Pt nanoparticles. This light-driven positioning of the cocatalyst close to the same positions where hot electrons are most efficiently generated and transferred represents a novel and simple method for synthesizing complex, self-optimized photocatalytic nanostructures with improved efficiency and selectivity.

Photochemical Resolution of a Thermally Inert Cyclometalated Ru(phbpy)(N-N)(Sulfoxide)+ Complex.

In this work a photosubstitution strategy is presented that can be used for the isolation of chiral organometallic complexes. A series of five cyclometalated complexes Ru(phbpy)(N-N)(DMSO-κS)](PF6) ([1]PF6-[5]PF6) were synthesized and characterized, where Hphbpy = 6'-phenyl-2,2'-bipyridyl, and N-N = bpy (2,2'-bipyridine), phen (1,10-phenanthroline), dpq (pyrazino[2,3- f][1,10]phenanthroline), dppz (dipyrido[3,2- a:2',3'- c]phenazine, or dppn (benzo[ i]dipyrido[3,2- a,2',3'- c]phenazine), respectively. Due to the asymmetry of the cyclometalated phbpy- ligand, the corresponding [Ru(phbpy)(N-N)(DMSO-κS)]+complexes are chiral. The exceptional thermal inertness of the Ru-S bond made chiral resolution of these complexes by thermal ligand exchange impossible. However, photosubstitution by visible light irradiation in acetonitrile was possible for three of the five complexes ([1]PF6-[3]PF6). Further thermal coordination of the chiral sulfoxide ( R)-methyl p-tolylsulfoxide to the photoproduct [Ru(phbpy)(phen)(NCMe)]PF6, followed by reverse phase HPLC, led to the separation and characterization of the two diastereoisomers of [Ru(phbpy)(phen)(MeSO(C7H7))]PF6, thus providing a new photochemical approach toward the synthesis of chiral cyclometalated ruthenium(II) complexes. Full photochemical, electrochemical, and frontier orbital characterization of the cyclometalated complexes [1]PF6-[5]PF6 was performed to explain why [4]PF6 and [5]PF6 are photochemically inert while [1]PF6-[3]PF6 perform selective photosubstitution.

Localized photodeposition of catalysts using nanophotonic resonances in silicon photocathodes.

Nanostructured semiconductors feature resonant optical modes that confine light absorption in specific areas called "hot spots". These areas can be used for localized extraction of the photogenerated charges, which in turn could drive chemical reactions for synthesis of catalytic materials. In this work, we use these nanophotonic hot spots in vertical silicon nanowires to locally deposit platinum nanoparticles in a photo-electrochemical system. The tapering angle of the silicon nanowires as well as the excitation wavelength are used to control the location of the hot spots together with the deposition sites of the platinum catalyst. A combination of finite difference time domain (FDTD) simulations with scanning electron microscopy image analysis showed a reasonable correlation between the simulated hot spots and the actual experimental localization and quantity of platinum atoms. This nanophotonic approach of driving chemical reactions at the nanoscale using the optical properties of the photo-electrode, can be very promising for the design of lithography-free and efficient hierarchical nanostructures for the generation of solar fuels.

Dynamics of dual-fluorescent polymersomes with durable integrity in living cancer cells and zebrafish embryos.

The long-term fate of biomedical nanoparticles after endocytosis is often only sparsely addressed in vitro and in vivo, while this is a crucial parameter to conclude on their utility. In this study, dual-fluorescent polyisobutylene-polyethylene glycol (PiB-PEG) polymersomes were studied for several days in vitro and in vivo. In order to optically track the vesicles' integrity, one fluorescent probe was located in the membrane and the other in the aqueous interior compartment. These non-toxic nanovesicles were quickly endocytosed in living A549 lung carcinoma cells but unusually slowly transported to perinuclear lysosomal compartments, where they remained intact and luminescent for at least 90 h without being exocytosed. Fluorescence-assisted flow cytometry indicated that after endocytosis, the nanovesicles were eventually degraded within 7-11 days. In zebrafish embryos, the polymersomes caused no lethality and were quickly taken up by the endothelial cells, where they remained fully intact for as long as 96 h post-injection. This work represents a novel case-study of the remarkable potential of PiB-PEG polymersomes as an in vivo bio-imaging and slow drug delivery platform.

Effects of the Bidentate Ligand on the Photophysical Properties, Cellular Uptake, and (Photo)cytotoxicity of Glycoconjugates Based on the [Ru(tpy)(NN)(L)]2+ Scaffold.

Ruthenium polypyridyl complexes have received widespread attention as potential chemotherapeutics in photodynamic therapy (PDT) and in photochemotherapy (PACT). Here, we investigate a series of sixteen ruthenium polypyridyl complexes with general formula [Ru(tpy)(N-N)(L)]+/2+ (tpy=2,2':6',2''-terpyridine, N-N=bpy (2,2'-bipyridine), phen (1,10-phenanthroline), dpq (pyrazino[2,3-f][1,10]phenanthroline), dppz (dipyrido[3,2-a:2',3'-c]phenazine, dppn (benzo[i]dipyrido[3,2-a:2',3'-c]phenazine), pmip (2-(4-methylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), pymi ((E)-N-phenyl-1-(pyridin-2-yl)methanimine), or azpy (2-(phenylazo)pyridine), L=Cl- or 2-(2-(2-(methylthio)ethoxy)ethoxy)ethyl-ß-d-glucopyranoside) and their potential for either PDT or PACT. We demonstrate that although increased lipophilicity is generally related to increased uptake of these complexes, it does not necessarily lead to increased (photo)cytotoxicity. However, the non-toxic complexes are excellent candidates as PACT carriers.

Light-responsive paper strips as CO-releasing material with a colourimetric response.

Carbon monoxide (CO) is known for its multifaceted role in human physiology, and molecules that release CO in a controlled way have been proposed as therapeutic drugs. In this work, a light-responsive CO-releasing molecule (CORM-Dabsyl) showed a strong colourimetric response upon photochemical CO-release, owing to the tight conjugation of a Mn(i) tricarbonyl centre to a dabsyl chromophoric ligand (L). Whereas the complex was very stable in the dark in nitrogen-purged aqueous media, CO-release was effectively triggered using 405 nm irradiation. CORM-Dabsyl, L and the inactive product iCORM-Dabsyl have been investigated by DFT and TD-DFT calculations. Only mild toxicity of CORM-Dabsyl was observed against LX-2 and HepaRG® human cell lines (IC50 ∼ 30 µM). Finally, to develop a CO storage and release material that is readily applicable to therapeutic situations, CORM-Dabsyl was loaded on low-cost and easily disposable paper strips, from which the light triggered CO-release was conveniently visible with the naked eye.

Red Light-Triggered CO Release from Mn2(CO)10 Using Triplet Sensitization in Polymer Nonwoven Fabrics.

Applicability of phototherapeutic CO-releasing molecules (photoCORMs) is limited because they are activated by harmful and poorly tissue-penetrating near-ultraviolet light. Here, a strategy is demonstrated to activate classical photoCORM Mn2(CO)10 using red light (635 nm). By mixing in solution a triplet photosensitizer (PS) with the photoCORM and shining red light, energy transfer occurs from triplet excited-state 3PS* to a photolabile triplet state of Mn2(CO)10, which, like under near-UV irradiation, led to complete release of carbonyls. Crucially, such "triplet-sensitized CO-release" occurred in solid-state materials: when PS and Mn2(CO)10 were embedded in electrospun nonwoven fabrics, CO was liberated upon irradiation with low-intensity red light (≤36 mW 635 nm).

A Red-Light-Activated Ruthenium-Caged NAMPT Inhibitor Remains Phototoxic in Hypoxic Cancer Cells.

We describe two water-soluble ruthenium complexes, [1]Cl2 and [2]Cl2 , that photodissociate to release a cytotoxic nicotinamide phosphoribosyltransferase (NAMPT) inhibitor with a low dose (21 J cm-2 ) of red light in an oxygen-independent manner. Using a specific NAMPT activity assay, up to an 18-fold increase in inhibition potency was measured upon red-light activation of [2]Cl2 , while [1]Cl2 was thermally unstable. For the first time, the dark and red-light-induced cytotoxicity of these photocaged compounds could be tested under hypoxia (1 % O2 ). In skin (A431) and lung (A549) cancer cells, a 3- to 4-fold increase in cytotoxicity was found upon red-light irradiation for [2]Cl2 , whether the cells were cultured and irradiated with 1 % or 21 % O2 . These results demonstrate the potential of photoactivated chemotherapy for hypoxic cancer cells, in which classical photodynamic therapy, which relies on oxygen activation, is poorly efficient.

Fluorinated Boronic Acid-Appended Pyridinium Salts and 19F NMR Spectroscopy for Diol Sensing.

The identification and discrimination of diols is of fundamental importance in medical diagnostics, such as measuring the contents of glucose in the urine of diabetes patients. Diol sensors are often based on fluorophore-appended boronic acids, but these severely lack discriminatory power and their response is one-dimensional. As an alternative strategy, we present the use of fluorinated boronic acid-appended pyridinium salts in combination with 19F NMR spectroscopy. A pool of 59 (bio)analytes was screened, containing monosaccharides, phosphorylated and N-acetylated sugars, polyols, carboxylic acids, nucleotides, and amines. The majority of analytes could be clearly detected and discriminated. In addition, glucose and fructose could be distinguished up to 1:9 molar ratio in mixtures. Crucially, the receptors feature high sensitivity and selectivity and are water-soluble, and their 19F-NMR analyte fingerprint is pH-robust, thereby making them particularly well-suited for medical application. Finally, to demonstrate this applicability, glucose could be detected in synthetic urine samples down to 1 mM using merely a 188 MHz NMR spectrometer.

Water-Dispersible Silica-Coated Upconverting Liposomes: Can a Thin Silica Layer Protect TTA-UC against Oxygen Quenching?

Light upconversion by triplet-triplet annihilation (TTA-UC) in nanoparticles has received considerable attention for bioimaging and light activation of prodrugs. However, the mechanism of TTA-UC is inherently sensitive for quenching by molecular oxygen. A potential oxygen protection strategy is the coating of TTA-UC nanoparticles with a layer of oxygen-impermeable material. In this work, we explore if (organo)silica can fulfill this protecting role. Three synthesis routes are described for preparing water-dispersible (organo)silica-coated red-to-blue upconverting liposomes. Their upconversion properties are investigated in solution and in A549 lung carcinoma cells. Although it was found that the silica offered no protection from oxygen in solution and after uptake in A549 cancer cells, upon drying of the silica-coated liposome dispersion in an excess of (organo)silica precursor, interesting liposome-silica nanocomposite materials were obtained that were capable of generating blue light upon red light excitation in air.

Temperature Dependence of Triplet-Triplet Annihilation Upconversion in Phospholipid Membranes.

Understanding the temperature dependency of triplet-triplet annihilation upconversion (TTA-UC) is important for optimizing biological applications of upconversion. Here the temperature dependency of red-to-blue TTA-UC is reported in a variety of neutral PEGylated phospholipid liposomes. In these systems a delicate balance between lateral diffusion rate of the dyes, annihilator aggregation, and sensitizer self-quenching leads to a volcano plot, with the maximum upconversion intensity occurring near the main order-disorder transition temperature of the lipid membrane.

d- Versus l-Glucose Conjugation: Mitochondrial Targeting of a Light-Activated Dual-Mode-of-Action Ruthenium-Based Anticancer Prodrug.

Light-activated ruthenium polypyridyl anticancer prodrugs often suffer from poor water solubility, poor selectivity, and/or ill-defined intracellular targets. Coordination of the d- or l-glucose thioether ligand 3 (2-(2-(2-(methylthio)ethoxy)ethoxy)ethyl-ß-glucopyranoside) to the highly lipophilic ruthenium complex [Ru(tpy)(dppn)(H2 O)]2+ ([1]2+ ; dppn=benzo[i]dipyrido-[3,2-a:2',3'-c]phenazine, tpy=2,2':6',2''-terpyridine) solved all these problems at once. The two enantiomers of [Ru(tpy)(dppn)(3)][PF6 ]2 , [d-2][PF6 ]2 and [l-2][PF6 ]2 , were soluble in water, which allowed the influence of the chirality of the glucose moiety on uptake, toxicity, and intracellular localization of the prodrug to be probed without changing any other physicochemical properties. Both compounds showed mild, but different, cytotoxicity in A549 (human lung carcinoma) and MCF-7 (human breast adenocarcinoma) cancer cells in the dark, whereas following low doses of visible light irradiation (3.1 J cm-2 at λ = 454 nm), a similar, but high cytotoxicity (EC50 < 1 µm), was observed. Irrespective of the chirality, both slightly emissive Ru complexes were found in the mitochondria, and two modes of action may contribute to light-induced cell death: 1) the glucose thioether ligand is photosubstituted by water, thus [1]2+ , which interacts with DNA at an exceptionally high 400:1 base pair/Ru ratio, is released; 2) both [1]2+ and [2]2+ produce massive amounts of singlet oxygen, which leads to very efficient photodynamic DNA cleavage.

Red Light Activation of Ru(II) Polypyridyl Prodrugs via Triplet-Triplet Annihilation Upconversion: Feasibility in Air and through Meat.

Triplet-triplet annihilation upconversion (TTA-UC) is a promising photophysical tool to shift the activation wavelength of photopharmacological compounds to the red or near-infrared wavelength domain, in which light penetrates human tissue optimally. However, TTA-UC is sensitive to dioxygen, which quenches the triplet states needed for upconversion. Here, we demonstrate not only that the sensitivity of TTA-UC liposomes to dioxygen can be circumvented by adding antioxidants, but also that this strategy is compatible with the activation of ruthenium-based chemotherapeutic compounds. First, red-to-blue upconverting liposomes were functionalized with a blue-light sensitive, membrane-anchored ruthenium polypyridyl complex, and put in solution in presence of a cocktail of antioxidants composed of ascorbic acid and glutathione. Upon red light irradiation with a medical grade 630 nm PDT laser, enough blue light was produced by TTA-UC liposomes under air to efficiently trigger full activation of the Ru-based prodrug. Then, the blue light generated by TTA-UC liposomes under red light irradiation (630 nm, 0.57 W/cm²) through different thicknesses of pork or chicken meat was measured, showing that TTA-UC still occurred even beyond 10 mm of biological tissue. Overall, the rate of activation of the ruthenium compound in TTA-UC liposomes using either blue or red light (1.6 W/cm²) through 7 mm of pork fillet were found comparable, but the blue light caused significant tissue damage, whereas red light did not. Finally, full activation of the ruthenium prodrug in TTA-UC liposomes was obtained under red light irradiation through 7 mm of pork fillet, thereby underlining the in vivo applicability of the activation-by-upconversion strategy.

Imaging Upconverting Polymersomes in Cancer Cells: Biocompatible Antioxidants Brighten Triplet-Triplet Annihilation Upconversion.

Light upconversion is a very powerful tool in bioimaging as it can eliminate autofluorescence, increase imaging contrast, reduce irradiation damage, and increase excitation penetration depth in vivo. In particular, triplet-triplet annihilation upconverting (TTA-UC) nanoparticles and liposomes offer high upconversion efficiency at low excitation power. However, TTA-UC is quenched in air by oxygen, which also leads to the formation of toxic singlet oxygen. In this work, polyisobutylene-monomethyl polyethylene glycol block copolymers are synthesized and used for preparing polymersomes that upconvert red light into blue light in absence of oxygen. In addition, it is demonstrated that biocompatible antioxidants such as l-ascorbate, glutathionate, l-histidine, sulfite, trolox, or even opti-MEM medium, can be used to protect the TTA-UC process in these polymersomes resulting in red-to-blue upconversion under aerobic conditions. Most importantly, this approach is also functional in living cells. When A549 lung carcinoma cells are treated with TTA-UC polymersomes in the presence of 5 × 10-3 m ascorbate and glutathionate, upconversion in the living cells is one order of magnitude brighter than that observed without antioxidants. These results propose a simple chemical solution to the issue of oxygen sensitivity of TTA-UC, which is of paramount importance for the technological advancement of this technique in biology.