Molecular Probing of the Microscopic Pressure at Contact Interfaces.

Obtaining insights into friction at the nanoscopic level and being able to translate these into macroscopic friction behavior in real-world systems is of paramount importance in many contexts, ranging from transportation to high-precision technology and seismology. Since friction is controlled by the local pressure at the contact it is important to be able to detect both the real contact area and the nanoscopic local pressure distribution simultaneously. In this paper, we present a method that uses planarizable molecular probes in combination with fluorescence microscopy to achieve this goal. These probes, inherently twisted in their ground states, undergo planarization under the influence of pressure, leading to bathochromic and hyperchromic shifts of their UV-vis absorption band. This allows us to map the local pressure in mechanical contact from fluorescence by exciting the emission in the long-wavelength region of the absorption band. We demonstrate a linear relationship between fluorescence intensity and (simulated) pressure at the submicron scale. This relationship enables us to experimentally depict the pressure distribution in multiasperity contacts. The method presented here offers a new way of bridging friction studies of the nanoscale model systems and practical situations for which surface roughness plays a crucial role.

XUV Absorption Spectroscopy and Photoconversion of a Tin-Oxo Cage Photoresist.

Extreme ultraviolet lithography has recently been introduced in high-volume production of integrated circuits for manufacturing the smallest features in high-end computer chips. Hybrid organic/inorganic materials are considered as the next generation of photoresists for this technology, but detailed knowledge about the response of such materials to the ionizing radiation used (13.5 nm, 92 eV) is still scarce. In the present work, we use broadband high-harmonic radiation in the energy range 22-70 eV for absorption spectroscopy and photobleaching (that is, the decrease of absorbance) of thin films of an n-butyltin oxo-cage, a representative of the class of metal-based EUV photoresist. The shape of the absorption spectrum in the range 22-92 eV matches well with the spectrum predicted using tabulated atomic cross sections. The photobleaching results are consistent with loss of the butyl side groups due to the breaking of Sn-C bonds following photoionization. Bleaching is strongest in the low-energy range (<40 eV), where the absorption is largely due to the carbon atoms in the organic groups. At higher energies (42-70 eV), absorption is dominated by the tin atoms, and since these remain in the film after photoconversion, the absorption change in this region is smaller. It is estimated that after prolonged irradiation (up to ∼3 J cm-2 in the range 22-40 eV) about 70% of the hydrocarbon groups are removed from the film. The rate of bleaching is high at the beginning of exposure, but it rapidly decreases with increasing conversion. We rationalize this using density functional theory calculations: the first Sn-C bonds are efficiently cleaved (quantum yield Φ ≈ 0.9), because the highest occupied molecular orbitals (HOMOs) (from which an electron is removed after photoionization) are located on Sn-C sigma bonds. In the photoproducts, the HOMO is localized on tin atoms that have lost their hydrocarbon group (formally reduced to the Sn(II) oxidation state), and holes formed on those tin atoms lead to less efficient cleavage reactions. Our results reveal the primary reaction steps following excitation with ionizing radiation of tin-oxo cages. Our methodology represents a systematic approach of studying and quantitatively assessing the performance of new photoresists and as such enables the development of future EUV photoresists.

Resolving Multi-Asperity Contacts at the Nanoscale through Super-Resolution Fluorescence Imaging.

Contact mechanics, spanning nanometer to tectonic scales, faces long-standing challenges arising from multiscale random roughness, which hinders experimental validation of theories. Understanding multi-asperity rough contacts is vital for addressing catastrophic consequences of these contacts failing such as earthquakes and for diverse technological applications. To visualize such contacts, we introduce a super-resolution microscopy method utilizing spontaneous millisecond ON/OFF fluorescence blinking of contact-sensitive molecular rotor molecules immobilized on a glass coverslip. This technique achieves ∼55 nm lateral imaging resolution for rough poly(methyl methacrylate) and glass spheres on glass contacts. For soft polymer spheres due to large plastic deformation, the resolution improvement does not significantly affect the area of real contact. However, for hard glass spheres, the real contact area is found to be 2.4 times smaller than that found by diffraction-limited imaging. This study highlights, through direct visualization, the impact of material stiffness on the nanoscale structure within the area of real contact.

Light-controlled morphological development of self-organizing bioinspired nanocomposites.

Nature's intricate biominerals inspire fundamental questions on self-organization and guide innovations towards functional materials. While advances in synthetic self-organization have enabled many levels of control, generating complex shapes remains difficult. Specifically, controlling morphologies during formation at the single micro/nanostructure level is the key challenge. Here, we steer the self-organization of barium carbonate nanocrystals and amorphous silica into complex nanocomposite morphologies by photogeneration of carbon dioxide (CO2) under ultraviolet (UV) light. Using modulations in the UV light intensity, we select the growth mode of the self-organization process inwards or outwards to form helical and coral-like morphologies respectively. The spatiotemporal control over CO2 photogeneration allows formation of different morphologies on pre-assigned locations, switching between different growth modes-to form for instance a coral on top of a helix or vice versa, and subtle sculpting and patterning of the nanocomposites during formation. These findings advance the understanding of these versatile self-organization processes and offer new prospects for tailored designs of functional materials using photochemically driven self-organization.

Soft X-ray absorption and fragmentation of tin-oxo cage photoresists.

"Tin-oxo cage" organometallic compounds are considered as photoresists for extreme ultraviolet (EUV) photolithography. To gain insight into their electronic structure and reactivity to ionizing radiation, we trapped bare gas-phase n-butyltin-oxo cage dications [(BuSn)12O14(OH)6]2+ in an ion trap and investigated their fragmentation upon soft X-ray photoabsorption by means of mass spectrometry. In complementary experiments, the tin-oxo cages with hydroxide and trifluoroacetate counter-anions were cast in thin films and studied using X-ray transmission spectroscopy. Quantum-chemical calculations were used to interpret the observed spectra. At the carbon K-edge, a distinct pre-edge absorption band can be attributed to transitions in which electrons are promoted from C1s orbitals to the lowest unoccupied molecular orbitals, which are delocalized orbitals with strong antibonding (Sn-C σ*) character. At higher energies, the most prominent resonant transitions involve C-C and C-H σ* valence states and Rydberg (3s and 3p) states. In the solid state, the onset of continuum ionization is shifted by ∼5 eV to lower energy with respect to the gas phase, due to the electrostatic effect of the counterions. The O K-edge also shows a pre-edge absorption, but it is devoid of any specific features, because there are many transitions from the different O1s orbitals to a large number of vacant orbitals. In the gas phase, formation of the parent [(BuSn)12O14(OH)6]3+ radical ion is not observed at the C K-edge nor at the O K-edge, because the loss of a butyl group from this species is very efficient. We do observe a number of triply charged photofragment ions, some of which have lost up to 5 butyl groups. Structures of these species are proposed based on quantum-chemical calculations, and pathways of formation are discussed. Our results provide insight into the electronic structure of alkyltin-oxo cages, which is a prerequisite for understanding their response to EUV photons and their performance as EUV photoresists.

Correction: UV and VUV-induced fragmentation of tin-oxo cage ions.

Correction for 'UV and VUV-induced fragmentation of tin-oxo cage ions' by Jarich Haitjema et al., Phys. Chem. Chem. Phys., 2021, 23, 20909-20918, https://doi.org/10.1039/D1CP03148A.

Super-resolution Fluorescence Imaging of Recycled Polymer Blends via Hydrogen Bond-Assisted Adsorption of a Nile Red Derivative.

A key challenge in the recycling of multilayer plastic films of polyethylene and polyamide, as typically used for food packaging, is to assess and control the phase separation of the two types of polymers in the recycled material, the specifics of which determine the mechanical strength of the recycled material. However, visualizing the polyamide-in-polyethylene domains with conventional fluorescence methods or electron microscopy is challenging. We present a new approach that combines the point accumulation in nanoscale topography (PAINT) super-resolution method with a newly synthesized Nile Red probe (diOHNR) as the fluorescent label. The molecule was modified to undergo a hydrogen bond-assisted interaction with the polyamide phase in the blend due to its two additional hydroxyl groups but preserves the spectral properties of Nile Red. As a result, the localization density of the probe in the PAINT image is 13 times larger at the polyamide phase than at the polyethylene phase, enabling quantitative evaluation of the spatial polyamide/polyethylene distribution down to the nanoscale. The method achieved a spatial resolution of 18.8 nm, and we found that over half of the polyamide particles in a recycled sample were smaller than the optical diffraction limit. Being able to image the blends with nanoscopic resolution can help to optimize the composition and mechanical properties of recycled materials and thus contribute to an increased reuse of plastics.

Molecular Probing of the Stress Activation Volume in Vapor Phase Lubricated Friction.

When two solid objects slide over each other, friction results from the interactions between the asperities of the (invariably rough) surfaces. Lubrication happens when viscous lubricants separate the two surfaces and carry the load such that solid-on-solid contacts are avoided. Yet, even small amounts of low-viscosity lubricants can still significantly lower friction through a process called boundary lubrication. Understanding the origin of the boundary lubricating effect is hampered by challenges in measuring the interfacial properties of lubricants directly between the two surfaces. Here, we use rigidochromic fluorescent probe molecules to measure precisely what happens on a molecular scale during vapor-phase boundary lubrication of a polymer bead-on-glass interface. The probe molecules have a longer fluorescence lifetime in a confined environment, which allows one to measure the area of real contact between rough surfaces and infer the shear stress at the lubricated interfaces. The latter is shown to be proportional to the inverse of the local interfacial free volume determined using the measured fluorescence lifetime. The free volume can then be used in an Eyring-type model as the stress activation volume, allowing to collapse the data of stress as a function of sliding velocity and partial pressure of the vapor phase lubricant. This shows directly that as more boundary lubricant is applied, larger clusters of lubricant molecules become involved in the shear process thereby lowering the friction.

Local Shearing Force Measurement during Frictional Sliding Using Fluorogenic Mechanophores.

When two macroscopic objects touch, the real contact typically consists of multiple surface asperities that are deformed under the pressure that holds the objects together. Application of a shear force makes the objects slide along each other, breaking the initial contacts. To investigate how the microscopic shear force at the asperity level evolves during the transition from static to dynamic friction, we apply a fluorogenic mechanophore to visualize and quantify the local interfacial shear force. When a contact is broken, the shear force is released and the molecules return to their dark state, allowing us to dynamically observe the evolution of the shear force at the sliding contacts. We find that the macroscopic coefficient of friction describes the microscopic friction well, and that slip propagates from the edge toward the center of the macroscopic contact area before sliding occurs. This allows for a local understanding of how surfaces start to slide.

Photosubstitution in a trisheteroleptic ruthenium complex inhibits conjunctival melanoma growth in a zebrafish orthotopic xenograft model.

In vivo data are rare but essential for establishing the clinical potential of ruthenium-based photoactivated chemotherapy (PACT) compounds, a new family of phototherapeutic drugs that are activated via ligand photosubstitution. Here a novel trisheteroleptic ruthenium complex [Ru(dpp)(bpy)(mtmp)](PF6)2 ([2](PF6)2, dpp = 4,7-diphenyl-1,10-phenanthroline, bpy = 2,2'-bipyridine, mtmp = 2-methylthiomethylpyridine) was synthesized and its light-activated anticancer properties were validated in cancer cell monolayers, 3D tumor spheroids, and in embryonic zebrafish cancer models. Upon green light irradiation, the non-toxic mtmp ligand is selectively cleaved off, thereby releasing a phototoxic ruthenium-based photoproduct capable notably of binding to nuclear DNA and triggering DNA damage and apoptosis within 24-48 h. In vitro, fifteen minutes of green light irradiation (21 mW cm-2, 19 J cm-2, 520 nm) were sufficient to generate high phototherapeutic indexes (PI) for this compound in a range of cancer cell lines including lung (A549), prostate (PC3Pro4), conjunctival melanoma (CRMM1, CRMM2, CM2005.1) and uveal melanoma (OMM1, OMM2.5, Mel270) cancer cell lines. The therapeutic potential of [2](PF6)2 was further evaluated in zebrafish embryo ectopic (PC3Pro4) or orthotopic (CRMM1, CRMM2) tumour models. The ectopic model consisted of red fluorescent PC3Pro4-mCherry cells injected intravenously (IV) into zebrafish, that formed perivascular metastatic lesions at the posterior ventral end of caudal hematopoietic tissue (CHT). By contrast, in the orthotopic model, CRMM1- and CRMM2-mCherry cells were injected behind the eye where they developed primary lesions. The maximally-tolerated dose (MTD) of [2](PF6)2 was first determined for three different modes of compound administration: (i) incubating the fish in prodrug-containing water (WA); (ii) injecting the prodrug intravenously (IV) into the fish; or (iii) injecting the prodrug retro-orbitally (RO) into the fish. To test the anticancer efficiency of [2](PF6)2, the embryos were treated 24 h after engraftment at the MTD. Optimally, four consecutive PACT treatments were performed on engrafted embryos using 60 min drug-to-light intervals and 90 min green light irradiation (21 mW cm-2, 114 J cm-2, 520 nm). Most importantly, this PACT protocol was not toxic to the zebrafish. In the ectopic prostate tumour models, where [2](PF6)2 showed the highest photoindex in vitro (PI > 31), the PACT treatment did not significantly diminish the growth of primary lesions, while in both conjunctival melanoma orthotopic tumour models, where [2](PF6)2 showed more modest photoindexes (PI ∼ 9), retro-orbitally administered PACT treatment significantly inhibited growth of the engrafted tumors. Overall, this study represents the first demonstration in zebrafish cancer models of the clinical potential of ruthenium-based PACT, here against conjunctival melanoma.

Molecular rotors to probe the local viscosity of a polymer glass.

We investigate the local viscosity of a polymer glass around its glass transition temperature by using environment-sensitive fluorescent molecular rotors embedded in the polymer matrix. The fluorescence of the rotors depends on the local viscosity, and measuring the fluorescence intensity and lifetime of the probe therefore allows us to measure the local free volume in the polymer glass when going through the glass transition. This also allows us to study the local viscosity and free volume when the polymer film is put under an external stress. We find that the film does not flow homogeneously but undergoes shear banding that is visible as a spatially varying free volume and viscosity.

Noncovalently bound and mechanically interlocked systems using pillar[n]arenes.

Pillar[n]arenes are pillar-shaped macrocyclic compounds owing to the methylene bridges linking the para-positions of the units. Owing to their unique pillar-shaped structures, these compounds exhibit various excellent properties compared with other cyclic host molecules, such as versatile functionality using various organic synthesis techniques, substituent-dependent solubility, cavity-size-dependent host-guest properties in organic media, and unit rotation along with planar chiral inversion. These advantages have enabled the high-yield synthesis and rational design of pillar[n]arene-based mechanically interlocked molecules (MIMs). In particular, new types of pillar[n]arene-based MIMs that can dynamically convert between interlocked and unlocked states through unit rotation have been produced. The highly symmetrical pillar-shaped structures of pillar[n]arenes result in simple NMR spectra, which are useful for studying the motion of pillar[n]arene wheels in MIMs and creating sophisticated MIMs with higher-order structures. The creation and application of polymeric MIMs based on pillar[n]arenes is also discussed.

Fluorine-Rich Zinc Oxoclusters as Extreme Ultraviolet Photoresists: Chemical Reactions and Lithography Performance.

The absorption of extreme ultraviolet (EUV) radiation by a photoresist strongly depends on its atomic composition. Consequently, elements with a high EUV absorption cross section can assist in meeting the demand for higher photon absorbance by the photoresist to improve the sensitivity and reduce the photon shot noise induced roughness. In this work, we enhanced the EUV absorption of the methacrylic acid ligands of Zn oxoclusters by introducing fluorine atoms. We evaluated the lithography performance of this fluorine-rich material as a negative tone EUV photoresist along with extensive spectroscopic and microscopic studies, providing deep insights into the underlying mechanism. UV-vis spectroscopy studies demonstrate that the presence of fluorine in the oxocluster enhances its stability in the thin films to the ambient atmosphere. However, the EUV photoresist sensitivity (D 50) of the fluorine-rich oxocluster is decreased compared to its previously studied methacrylic acid analogue. Scanning transmission X-ray microscopy and in situ X-ray photoelectron spectroscopy in combination with FTIR and UV-vis spectroscopy were used to gain insights into the chemical changes in the material responsible for the solubility switch. The results support decarboxylation of the ligands and subsequent radical-induced polymerization reactions in the thin film upon EUV irradiation. The rupture of carbon-fluorine bonds via dissociative electron attachment offers a parallel way of generating radicals. The mechanistic insights obtained here will be applicable to other hybrid materials and potentially pave the way for the development of EUV materials with better performance.

Light-Controlled Nucleation and Shaping of Self-Assembling Nanocomposites.

Controlling self-assembly of nanocomposites is a fundamental challenge with exciting implications for next-generation advanced functional materials. Precursors for composites can be generated photochemically, but limited insight in the underlying processes has hindered precise hands-on guidance. In this study, light-controlled nucleation and growth is demonstrated for self-assembling composites according to precise user-defined designs. Carbonate is generated photochemically with UV light to steer the precipitation of nanocomposites of barium carbonate nanocrystals and amorphous silica (BaCO3 /SiO2 ). Using a custom-built optical setup, the self-assembly process is controlled by optimizing the photogeneration, diffusion, reaction, and precipitation of the carbonate species, using the radius and intensity of the UV-light irradiated area and reaction temperature. Exploiting this control, nucleation is induced and the contours and individual features of the growing composite are sculpted according to micrometer-defined light patterns. Moreover, moving light patterns are exploited to create a constant carbonate concentration at the growth front to draw lines of nanocomposites with constant width over millimeters with micrometer precision. Light-directed generation of local gradients opens previously unimaginable opportunities for guiding self-assembly into functional materials.

Shorter Alkyl Chains Enhance Molecular Diffusion and Electron Transfer Kinetics between Photosensitisers and Catalysts in CO2 -Reducing Photocatalytic Liposomes.

Covalent functionalisation with alkyl tails is a common method for supporting molecular catalysts and photosensitisers onto lipid bilayers, but the influence of the alkyl chain length on the photocatalytic performances of the resulting liposomes is not well understood. In this work, we first prepared a series of rhenium-based CO2 -reduction catalysts [Re(4,4'-(Cn H2n+1 )2 -bpy)(CO)3 Cl] (ReCn ; 4,4'-(Cn H2n+1 )2 -bpy=4,4'-dialkyl-2,2'-bipyridine) and ruthenium-based photosensitisers [Ru(bpy)2 (4,4'-(Cn H2n+1 )2 -bpy)](PF6 )2 (RuCn ) with different alkyl chain lengths (n=0, 9, 12, 15, 17, and 19). We then prepared a series of PEGylated DPPC liposomes containing RuCn and ReCn , hereafter noted Cn , to perform photocatalytic CO2 reduction in the presence of sodium ascorbate. The photocatalytic performance of the Cn liposomes was found to depend on the alkyl tail length, as the turnover number for CO (TON) was inversely correlated to the alkyl chain length, with a more than fivefold higher CO production (TON=14.5) for the C9 liposomes, compared to C19 (TON=2.8). Based on immobilisation efficiency quantification, diffusion kinetics, and time-resolved spectroscopy, we identified the main reason for this trend: two types of membrane-bound RuCn species can be found in the membrane, either deeply buried in the bilayer and diffusing slowly, or less buried with much faster diffusion kinetics. Our data suggest that the higher photocatalytic performance of the C9 system is due to the higher fraction of the more mobile and less buried molecular species, which leads to enhanced electron transfer kinetics between RuC9 and ReC9 .

Fluorescent Labeling to Investigate Nanopatterning Processes in Extreme Ultraviolet Lithography.

Extreme ultraviolet (EUV) lithography uses 13.5 nm light to reach the sub-20 nm resolution. However, the process of pattern formation induced by this high-energy light is not well-understood. In this work, we provide an inorganic EUV photoresist with fluorescence properties by introducing a carbazole derivative as a ligand, and we study its effect on the patterning process. Using the fluorescence properties, changes in the emission of the material after EUV exposure could be tracked by means of spectroscopy and microscopy. The resist sensitivity was substantially reduced by the incorporation of the carbazole benzoate ligands, which is attributed to hole trapping and steric hindrance. After EUV irradiation of the resist films, infrared, UV-visible absorption, and fluorescence spectroscopies showed that the carbazole units were still mostly intact, although their fluorescence intensity was lowered. Our work shows that fluorescent labeling can provide relevant mechanistic insights in the patterning process of resists, potentially with a molecular resolution.

Fluorescent Liquid Tetrazines.

Tetrazines with branched alkoxy substituents are liquids at ambient temperature that despite the high chromophore density retain the bright orange fluorescence that is characteristic of this exceptional fluorophore. Here, we study the photophysical properties of a series of alkoxy-tetrazines in solution and as neat liquids. We also correlate the size of the alkoxy substituents with the viscosity of the liquids. We show using time-resolved spectroscopy that intersystem crossing is an important decay pathway competing with fluorescence, and that its rate is higher for 3,6-dialkoxy derivatives than for 3-chloro-6-alkoxytetrazines, explaining the higher fluorescence quantum yields for the latter. Quantum chemical calculations suggest that the difference in rate is due to the activation energy required to distort the tetrazine core such that the nπ*S1 and the higher-lying ππ*T2 states cross, at which point the spin-orbit coupling exceeding 10 cm-1 allows for efficient intersystem crossing to occur. Femtosecond time-resolved anisotropy studies in solution allow us to measure a positive relationship between the alkoxy chain lengths and their rotational correlation times, and studies in the neat liquids show a fast decay of the anisotropy consistent with fast exciton migration in the neat liquid films.

UV and VUV-induced fragmentation of tin-oxo cage ions.

Photoresist materials are being optimized for the recently introduced Extreme Ultraviolet (EUV) photolithographic technology. Organometallic compounds are potential candidates for replacing the ubiquitous polymer-based chemically amplified resists. Tin (Sn) has a particularly large absorption cross section for EUV light (13.5 nm, 92 eV), which could lead to a lower required EUV dose for achieving the desired solubility change (improved sensitivity). However, the fundamental interaction between organometallic materials and higher energy photons is poorly understood. In this work, we exposed n-butyltin-oxo cage dications (M2+) in the gas phase to photons in the energy range 4-35 eV to explore their fundamental photoreactivity. Photoproducts were detected using mass spectrometry. Homolytic cleavage of tin-carbon bonds was observed for all photon energies above the onset of electronic absorption at ∼5 eV (∼250 nm), leading to photoproducts which have lost one or more of the attached butyl groups (Bu). Above 12 eV (<103 nm), dissociative photoionization occurred for the dication (M2+), competing with the neutral loss channels. The photoionization threshold is lowered by approximately 2 eV when one counterion (triflate, OTf- or tosylate, OTs-) is attached to the tin-oxo cage (MOTf+ and MOTs+). This threshold is expected to be even lower if each tin-oxo cage is attached to two counterions, as is the case in a solid film of tin-oxo cages. Addition of counterions also affected the fragmentation pathways; photoexcitation of (MX)+ (X = counterion, OTf or OTs) always led to formation of (MX-2Bu)+ rather than (MX-Bu)+. MOTs+ was much more reactive than MOTf+ in terms of reaction products per absorbed photon. A possible explanation for this is proposed, which involves the counterion reacting with the initially formed tin-based radical.

Intracellular Dynamic Assembly of Deep-Red Emitting Supramolecular Nanostructures Based on the Pt Pt Metallophilic Interaction.

Many drug delivery systems end up in the lysosome because they are built from covalent or kinetically inert supramolecular bonds. To reach other organelles, nanoparticles hence need to either be made from a kinetically labile interaction that allows re-assembly of the nanoparticles inside the cell following endocytic uptake, or, be taken up by a mechanism that short-circuits the classical endocytosis pathway. In this work, the intracellular fate of nanorods that self-assemble via the Pt…Pt interaction of cyclometalated platinum(II) compounds, is studied. These deep-red emissive nanostructures (638 nm excitation, ≈700 nm emission) are stabilized by proteins in cell medium. Once in contact with cancer cells, they cross the cell membrane via dynamin- and clathrin-dependent endocytosis. However, time-dependent confocal colocalization and cellular electron microscopy demonstrate that they directly move to mitochondria without passing by the lysosomes. Altogether, this study suggests that Pt…Pt interaction is strong enough to generate emissive, aggregated nanoparticles inside cells, but labile enough to allow these nanostructures to reach the mitochondria without being trapped in the lysosomes. These findings open new venues to the development of bioimaging nanoplatforms based on the Pt…Pt interaction.

Disentangling Nano- and Macroscopic Viscosities of Aqueous Polymer Solutions Using a Fluorescent Molecular Rotor.

The macroscopic viscosity of polymer solutions in general differs strongly from the viscosity at the nanometer scale, and the relation between the two can be complicated. To investigate this relation, we use a fluorescent molecular rotor that probes the local viscosity of its molecular environment. For a range of chain lengths and concentrations, the dependence of the fluorescence on the macroscopic viscosity is well described by the classical Förster-Hoffmann (FH) equation, but the value of the FH exponent depends on the polymer chain length. We show that all data can be collapsed onto a master curve by plotting the fluorescence versus polymer concentration, which we explain in terms of the characteristic mesh size of the polymer solution. Using known scaling laws for polymers then allows us to quantitatively explain the relation between the FH exponent and the polymer chain length, allowing us to link the nano- to the macroviscosity.