Anomalously bright single-molecule upconversion electroluminescence.

Efficient upconversion electroluminescence is highly desirable for a broad range of optoelectronic applications, yet to date, it has been reported only for ensemble systems, while the upconversion electroluminescence efficiency remains very low for single-molecule emitters. Here we report on the observation of anomalously bright single-molecule upconversion electroluminescence, with emission efficiencies improved by more than one order of magnitude over previous studies, and even stronger than normal-bias electroluminescence. Intuitively, the improvement is achieved via engineering the energy-level alignments at the molecule-substrate interface so as to activate an efficient spin-triplet mediated upconversion electroluminescence mechanism that only involves pure carrier injection steps. We further validate the intuitive picture with the construction of delicate electroluminescence diagrams for the excitation of single-molecule electroluminescence, allowing to readily identify the prerequisite conditions for producing efficient upconversion electroluminescence. These findings provide deep insights into the microscopic mechanism of single-molecule upconversion electroluminescence and organic electroluminescence in general.

Heterostructured MoO3 Anchored Defect-Rich NiFe-LDH/NF as a Robust Self-Supporting Electrocatalyst for Overall Water Splitting.

The rational design of inexpensive metal electrocatalysts with exciting catalytic activity for overall water splitting (OWS) remains a significant challenge. Heterostructures of NiFe layered double hydroxides (NiFe-LDHs) with abundant oxygen defects and tunable electronic properties have garnered considerable attention. Here, a self-supporting heterostructured catalyst (named MoO3/NiFe-NF) is synthesized via a hydrothermal method to grow NiFe-LDH with oxygen vacancies (OV) in situ on inexpensive nickel foam (NF). Subsequently, MoO3 is anchored and grown on the surface of NiFe-LDH by electrodeposition. The obtained catalysts achieved outstanding oxygen/hydrogen evolution reaction (OER/HER, 212 mV/85 mV@10 mA cm-2) performance in 1 m KOH. Additionally, when MoO3/NiFe-NF is utilized as the cathode and anode in OWS, a current density of 10 mA cm-2 can be obtained as an ultralow battery voltage of 1.43 V, a significantly lower value compared to the commercial electrolyzer incorporating Pt/C and IrO2 electrode materials. Finally, density functional theory (DFT) calculations and advanced spectroscopy technology are conducted to reveal the effects of heterojunctions and OV on the internal electronic structure of the electrical catalysts. Mainly, the present study provides a novel tactic for the rational design of remarkable, low-cost NiFe-LDH electrocatalysts with heterostructures for OWS.

Back focal plane imaging for light emission from a tunneling junction in a low-temperature ultrahigh-vacuum scanning tunneling microscope.

We report the design and realization of the back focal plane (BFP) imaging for the light emission from a tunnel junction in a low-temperature ultrahigh-vacuum (UHV) scanning tunneling microscope (STM). To achieve the BFP imaging in a UHV environment, a compact "all-in-one" sample holder is designed and fabricated, which allows us to integrate the sample substrate with the photon collection units that include a hemisphere solid immersion lens and an aspherical collecting lens. Such a specially designed holder enables the characterization of light emission both within and beyond the critical angle and also facilitates the optical alignment inside a UHV chamber. To test the performance of the BFP imaging system, we first measure the photoluminescence from dye-doped polystyrene beads on a thin Ag film. A double-ring pattern is observed in the BFP image, arising from two kinds of emission channels: strong surface plasmon coupled emissions around the surface plasmon resonance angle and weak transmitted fluorescence maximized at the critical angle, respectively. Such an observation also helps to determine the emission angle for each image pixel in the BFP image and, more importantly, proves the feasibility of our BFP imaging system. Furthermore, as a proof-of-principle experiment, electrically driven plasmon emissions are used to demonstrate the capability of the constructed BFP imaging system for STM induced electroluminescence measurements. A single-ring pattern is obtained in the BFP image, which reveals the generation and detection of the leakage radiation from the surface plasmon propagating on the Ag surface. Further analyses of the BFP image provide valuable information on the emission angle of the leakage radiation, the orientation of the radiating dipole, and the plasmon wavevector. The UHV-BFP imaging technique demonstrated here opens new routes for future studies on the angular distributed emission and dipole orientation of individual quantum emitters in UHV.

Fluctuating magnetic droplets immersed in a sea of quantum spin liquid.

The search of quantum spin liquid (QSL), an exotic magnetic state with strongly fluctuating and highly entangled spins down to zero temperature, is a main theme in current condensed matter physics. However, there is no smoking gun evidence for deconfined spinons in any QSL candidate so far. The disorders and competing exchange interactions may prevent the formation of an ideal QSL state on frustrated spin lattices. Here we report comprehensive and systematic measurements of the magnetic susceptibility, ultralow-temperature specific heat, muon spin relaxation (µSR), nuclear magnetic resonance (NMR), and thermal conductivity for NaYbSe2 single crystals, in which Yb3+ ions with effective spin-1/2 form a perfect triangular lattice. All these complementary techniques find no evidence of long-range magnetic order down to their respective base temperatures. Instead, specific heat, µSR, and NMR measurements suggest the coexistence of quasi-static and dynamic spins in NaYbSe2. The scattering from these quasi-static spins may cause the absence of magnetic thermal conductivity. Thus, we propose a scenario of fluctuating ferrimagnetic droplets immersed in a sea of QSL. This may be quite common on the way pursuing an ideal QSL, and provides a brand new platform to study how a QSL state survives impurities and coexists with other magnetically ordered states.

Classification of Histological Types and Stages in Non-small Cell Lung Cancer Using Radiomic Features Based on CT Images.

Non-invasive diagnostic method based on radiomic features in patients with non-small cell lung cancer (NSCLC) has attracted attention. This study aimed to develop a CT image-based model for both histological typing and clinical staging of patients with NSCLC. A total of 309 NSCLC patients with 537 CT series from The Cancer Imaging Archive (TCIA) database were included in this study. All patients were randomly divided into the training set (247 patients, 425 CT series) and testing set (62 patients, 112 CT series). A total of 107 radiomic features were extracted. Four classifiers including random forest, XGBoost, support vector machine, and logistic regression were used to construct the classification model. The classification model had two output layers: histological type (adenocarcinoma, squamous cell carcinoma, and large cell) and clinical stage (I, II, and III) of NSCLC patients. The area under the receiver operating characteristic curve (AUC), accuracy, sensitivity, specificity, positive predictive value (PPV), and negative predictive value (NPV) with 95% confidence interval (CI) were utilized to evaluate the performance of the model. Seven features were selected for inclusion in the classification model. The random forest model had the best classification ability compared with other classifiers. The AUC of the RF model for histological typing and clinical staging of NSCLC patients in the testing set was 0.700 (95% CI, 0.641-0.759) and 0.881 (95% CI, 0.842-0.920), respectively. The CT image-based radiomic feature model had good classification ability for both histological typing and clinical staging of patients with NSCLC.

Wavelike electronic energy transfer in donor-acceptor molecular systems through quantum coherence.

Quantum-coherent intermolecular energy transfer is believed to play a key role in light harvesting in photosynthesis and photovoltaics. So far, a direct, real-space demonstration of quantum coherence in donor-acceptor systems has been lacking because of the fragile quantum coherence in lossy molecular systems. Here, we precisely control the separations in well-defined donor-acceptor model systems and unveil a transition from incoherent to coherent electronic energy transfer. We monitor the fluorescence from the heterodimers with subnanometre resolution through scanning tunnelling microscopy induced luminescence. With decreasing intermolecular distance, the dipole coupling strength increases and two new emission peaks emerge: a low-intensity peak blueshifted from the donor emission, and an intense peak redshifted from the acceptor emission. Spatially resolved spectroscopic images of the redshifted emission exhibit a σ antibonding-like pattern and thus indicate a delocalized nature of the excitonic state over the whole heterodimer due to the in-phase superposition of molecular excited states. These observations suggest that the exciton can travel coherently through the whole heterodimer as a quantum-mechanical wavepacket. In our model system, the wavelike quantum-coherent transfer channel is three times more efficient than the incoherent channel.

Glucagon-like peptide-1 receptor agonist liraglutide therapy for psoriasis patients with type 2 diabetes: a randomized-controlled trial.

OBJECTIVE: There were some clinical studies on GLP-1R agonist liraglutide therapy for psoriasis patients with type 2 diabetes, but there is a lack of randomized controlled trials and the mechanism of which remains unclear. METHOD: A total of 25 psoriasis patients with type 2 diabetes were randomized 1: 1 divided into the control group (n = 13) or liraglutide group (n = 12) for 12 weeks. We determined the PASI, the DLQI, histopathology of psoriasis skin, and the expression of IL-17, IL-23, and TNF-α in the psoriasis skin. RESULTS: After 12 weeks of treatment, the mean DLQI of the treatment group decreased from 22.00 ± 5.85 to 3.82 ± 3.60 (p < .05). Compared to week 12, the change in the baseline value of PASI and DLQI in the treatment group showed a significant difference compared with the control group (p < .05). The pathological changes of psoriasis skin and the expression of IL-17, IL-23, TNF-α in the psoriasis skin were improved in the treatment group. No serious adverse events occurred. CONCLUSION: The skin lesions in psoriasis patients with type 2 diabetes were significantly improved after treatment with liraglutide, which may be related to the inhibition of the expression of inflammatory factors such as IL-23, IL-17, and TNF-α.

Probing intramolecular vibronic coupling through vibronic-state imaging.

Vibronic coupling is a central issue in molecular spectroscopy. Here we investigate vibronic coupling within a single pentacene molecule in real space by imaging the spatial distribution of single-molecule electroluminescence via highly localized excitation of tunneling electrons in a controlled plasmonic junction. The observed two-spot orientation for certain vibronic-state imaging is found to be evidently different from the purely electronic 0-0 transition, rotated by 90°, which reflects the change in the transition dipole orientation from along the molecular short axis to the long axis. Such a change reveals the occurrence of strong vibronic coupling associated with a large Herzberg-Teller contribution, going beyond the conventional Franck-Condon picture. The emergence of large vibration-induced transition charges oscillating along the long axis is found to originate from the strong dynamic perturbation of the anti-symmetric vibration on those carbon atoms with large transition density populations during electronic transitions.

What can single-molecule Fano resonance tell?

In this work, we showcase applications of single-molecule Fano resonance (SMFR) measurements beyond the determination of molecular excitonic energy and associated dipole orientation. We use the SMFR measurement to probe the local influence of a man-made single chlorine vacancy on the molecular transition of a single zinc phthalocyanine, which clearly reveals the lifting-up of the double degeneracy of the excited states due to defect-induced configurational changes. Furthermore, time-trace SMFR measurements at different excitation voltages are used to track the tautomerization process in a free-base phthalocyanine. Different behaviors in switching between two inner-hydrogen configurations are observed with decreasing voltages, which helps to reveal the underlying tautomerization mechanism involving both the molecular electronic excited states and vibrational excited states in the ground state.

Rete Ridges in Eyelid Margin and Inflammatory Cytokines in Meibomian Gland Dysfunction Associated with Dry Eye Symptom.

PURPOSE: To evaluate the morphology and function of rete ridges in eyelid margin and inflammatory cytokines in meibomian gland dysfunction (MGD) associated with dry eye symptom. METHODS: A total of 63 subjects with OSDI score ≥13 were enrolled in MGD group and no-MGD group. Main measurements included tear cytokines levels and the rete ridges morphology. RESULTS: Meibomian gland loss (MGL), corneal staining score (CSS), and IL-6 and TNF-α increased, meibomian gland secretion (MGS) decreased, the density of the rete ridges was lower, the longest diameters and shortest diameters of the rete ridges were longer in MGD group. The MGD group showed a negative correlation between MGL and BUT and MGS, but it showed a positive correlation with CSS. CSS was negatively correlated with IL-6. LLT was negatively correlated with IL-2 and IL-4. The shortest diameters of rete ridges in eyelid margin had a significant positive correlation with IL-2, IL-4, IL-10, and IFN-γ levels. CONCLUSION: Change of meibomian gland function and the rete ridges morphology might have some correlation with the injury to ocular surface. Some inflammatory cytokines were correlated with the change of the rete ridges morphology, which might in turn affect the ocular surface function.

Electrically Driven Single-Photon Superradiance from Molecular Chains in a Plasmonic Nanocavity.

We demonstrate single-photon superradiance from artificially constructed nonbonded zinc-phthalocyanine molecular chains of up to 12 molecules. We excite the system via electron tunneling in a plasmonic nanocavity and quantitatively investigate the interaction of the localized plasmon with single-exciton superradiant states resulting from dipole-dipole coupling. Dumbbell-like patterns obtained by subnanometer resolved spectroscopic imaging disclose the coherent nature of the coupling associated with superradiant states while second-order photon correlation measurements demonstrate single-photon emission. The combination of spatially resolved spectral measurements with theoretical considerations reveals that nanocavity plasmons dramatically modify the linewidth and intensity of emission from the molecular chains, but they do not dictate the intrinsic coherence of the superradiant states. Our studies shed light on the optical properties of molecular collective states and their interaction with nanoscopically localized plasmons.

Spin-Triplet-Mediated Up-Conversion and Crossover Behavior in Single-Molecule Electroluminescence.

Scanning-tunneling-microscope-induced light emission serves as a powerful approach in revealing and manipulating the optical properties of molecular species, intermolecular energy transfer, and plasmon-molecule coupling. Earlier studies have established the existence of molecular up-conversion electroluminescence in diverse situations, but the underlying microscopic mechanisms are still under active debate, dominated by intermolecular triplet-triplet annihilation and plasmonic pumping. Here we report on the experimental realization of up-conversion electroluminescence from a prototypical single phthalocyanine molecule, allowing us to unambiguously rule out mechanisms based on intermolecular coupling and also offering unprecedented opportunities to elucidate much richer characteristics unforeseen in previous studies. In particular, the bias-dependent emission intensity displays three distinct regions with different nonlinear current dependences, which can be attributed to crossover behavior caused by the interplay between inelastic electron scattering and carrier-injection processes. We also develop a microscopic description to capture the essential physics involved in up-conversion electroluminescence mediated by a proper intermediate spin-triplet state.

Treatment with liraglutide, a glucagon-like peptide-1 analogue, improves effectively the skin lesions of psoriasis patients with type 2 diabetes: A prospective cohort study.

BACKGROUND: It has been reported that GLP-1 analogue can improve the skin lesions of psoriasis. However further research is needed to confirm that finding. OBJECTIVE: The study can provide further data regarding the efficacy and safety of GLP-1 analogue liraglutide in the treatment of psoriasis patients with type 2 diabetes. METHODS: We recruit 7 psoriasis patients with type 2 diabetes, and use hypodermic injection with liraglutide1.8 mg. In 12 weeks of treatment, we estimate the difference of before and after respectively, likeBMI, waist circumference, fasting blood glucose, fasting C-peptide, HbA1c, blood lipid levels, CRP, PASI, DLQI, skin tissue and pathological analysis of psoriasis. RESULTS: After 12 weeks of treatment, the mean value of PASI decreased from 15.7 ±â€¯11.8 to 2.2 ±â€¯3.0 (P = 0.03), while the DLQI decreased from 21.8 ±â€¯6 to 4.1 ±â€¯3.9 (P = 0.001). HbA1c was significantly improved after 12 weeks of treatment, decreased to 6.4 ±â€¯0.8% (P = 0.04), the BMI decreased to 21 ±â€¯3 kg m-2 (P < 0.01), and the waist circumference was also significantly improved to 83 ±â€¯1 cm (P < 0.05). And 12 weeks after, the fasting C-peptide levels increased to 1.9 ±â€¯0.5 ng/ml (P = 0.006), HOMA - IR fell to 1.6 ±â€¯0.6 (P = 0.03). Histological analysis showed a reduction in epidermal thickness after treatment. The mean PASI decreased from 15.7 (1.5-31.3) to 2.0 (0.3-8.7) (P = 0.03), the DLQI decreased from 22 (8-27) to 4 (0-10) (P = 0.001). CONCLUSION: GLP-1 analogueliraglutide can improve the skin lesions of psoriasis patients with type 2 diabetes effectively, especially for extremely severe psoriasis patients. Its therapeutic effect may be related to anti-inflammatory, hypoglycemic and reducing weight.

Substance P inhibits high urea-induced apoptosis through the AKT/GSK-3ß pathway in human corneal epithelial cells.

To investigate the effect of substance P (SP) on human corneal epithelial cells (HCECs) that have been stressed by a high urea environment and to determine the relationship between SP and the protein kinase B (AKT)/glycogen synthase kinase-3ß (GSK-3ß) signaling pathway. An in vitro model of chronic renal failure (CRF)-related dry eye was used to study HCECs that were treated with high urea concentrations. Cell proliferation was assayed using a cell counting kit-8 test. Besides, cell apoptosis was evaluated by flow cytometry. Furthermore, the effects of SP and the AKT inhibitor perifosine on the urea-treated HCECs were examined using immunofluorescence, quantitative real time polymerase chain reaction (qRT-PCR), and Western blot analysis. SP markedly reduced the number of apoptotic HCECs and decreased the cleaved caspase-3 expression levels while contributing to increased cellular proliferation (P < 0.05). The Western blot analysis and qRT-PCR experiments revealed that SP significantly increased the expression of p-AKT and p-GSK-3ß (P < 0.05); additionally, these increases were attenuated after the perifosine inhibition of the AKT signaling pathway (P < 0.05). These in vitro experiments demonstrated that SP may protect against the apoptotic damage of HCECs caused by the high urea condition. The underlying mechanism may be related to the activation of the AKT/GSK-3ß signaling pathway.

The Role of the RhoA/ROCK Signaling Pathway in Mechanical Strain-Induced Scleral Myofibroblast Differentiation.

Purpose: Biomechanical properties changes and α-smooth muscle actin (α-SMA) overexpression are involved in myopia scleral remodeling. However, interactions between altered tissue biomechanics and cellular signaling that sustain scleral remodeling have not been well defined. We determine the mechanisms of mechanotransduction in the regulation of α-SMA expression during myopia scleral remodeling. Methods: Guinea pigs were used to establish a form-deprivation myopia (FDM) model. Protein profiles in myopic sclera were examined using tandem mass spectrometry. Ras homolog gene family member A (RhoA) and α-SMA expressions were confirmed using quantitative (q) RT-PCR and Western blotting. Scleral fibroblasts were cultured and subjected to 4% cyclic strain. Levels of RhoA, rho-associated protein kinase-2 (ROCK2), myocardin-related transcription factor-A (MRTF-A), serum response factor (SRF), and α-SMA were determined by qRT-PCR and Western blotting in groups with or without the RhoA siRNA or ROCK inhibitor Y27632. MRTF-A and α-SMA were evaluated by confocal immunofluorescent microscopy and myofibroblasts were enumerated using flow cytometry. Results: mRNA and protein levels of RhoA and α-SMA were significantly increased in the FDM eyes after 4 weeks of form-deprivation treatment. The 4% static strain increased expressions of RhoA, ROCK2, MRTF-A, SRF, and α-SMA as well as nuclear translocalization of MRTF-A in scleral fibroblasts compared to those without strain stimulation. Additionally, the percentage of myofibroblasts increased after strain stimulation. Conversely, inhibition of RhoA or ROCK2 reversed the strain-induced α-SMA expression and myofibroblast ratio. Conclusions: Mechanical strain activated RhoA signaling and scleral myofibroblast differentiation. Strain also mediated myofibroblast differentiation via the RhoA/ROCK2-MRTF-A/SRF pathway. These findings provided evidence for a mechanical strain-induced RhoA/ROCK2 pathway that may contribute to myopia scleral remodeling.

Spin-Glass Ground State in a Triangular-Lattice Compound YbZnGaO_{4}.

We report on comprehensive results identifying the ground state of a triangular-lattice structured YbZnGaO_{4} as a spin glass, including no long-range magnetic order, prominent broad excitation continua, and the absence of magnetic thermal conductivity. More crucially, from the ultralow-temperature ac susceptibility measurements, we unambiguously observe frequency-dependent peaks around 0.1 K, indicating the spin-glass ground state. We suggest this conclusion holds also for its sister compound YbMgGaO_{4}, which is confirmed by the observation of spin freezing at low temperatures. We consider disorder and frustration to be the main driving force for the spin-glass phase.

Crosslinking Enzyme Lysyl Oxidase Modulates Scleral Remodeling in Form-Deprivation Myopia.

PURPOSE: Scleral remodeling causes the excessive ocular elongation that underlies myopia. Lysyl oxidase (LOX), a copper-containing amine oxidase, can catalyze collagen and elastin crosslinking. The purpose of this study was to investigate the role of LOX in scleral remodeling in form-deprivation myopia (FDM). METHODS: Seventy-five guinea pigs were randomly divided into five groups as follows: a normal control group, an FDM group, an FDM plus ß-aminopropionitrile (BAPN) group, an FDM plus TGF-ß1 (TGF-ß1) group, and an FDM plus vehicle group. A translucent diffuser was used to induce FDM, and intravitreal injection was used to administer BAPN, TGF-ß1 or vehicle. The scleral LOX and collagen gene and protein levels and the posterior scleral ultrastructure and biomechanics were measured. RESULTS: In the FDM group, both the scleral LOX and collagen gene and protein levels were significantly lower than those in the control eyes. The collagen fibril diameters were significantly decreased in the FDM group compared with the diameters in the control group. A significant decrease in LOX gene and protein expression was observed after BAPN injection, and an increase was observed after TGF-ß1 treatment compared with the levels in the FDM group. Additionally, the scleral collagen fibrils were significantly decreased in the BAPN-treated eyes but increased in the TGF-ß1-treated eyes compared with the FDM eyes. The ultimate stress and Young's modulus of the sclera were lowest in the BAPN group, followed by the FDM group and the TGF-ß1 group. The ultimate strain (%) of the sclera was lowest in the TGF-ß1 group, followed by the FDM group and the BAPN group. CONCLUSION: LOX expression was significantly lowered in myopic sclera. Modulating LOX expression induced a change in both the scleral collagen fibril diameter and the scleral biomechanics. Therefore, LOX may play a key role in the myopia scleral remodeling procedure.

Electrically driven single-photon emission from an isolated single molecule.

Electrically driven molecular light emitters are considered to be one of the promising candidates as single-photon sources. However, it is yet to be demonstrated that electrically driven single-photon emission can indeed be generated from an isolated single molecule notwithstanding fluorescence quenching and technical challenges. Here, we report such electrically driven single-photon emission from a well-defined single molecule located inside a precisely controlled nanocavity in a scanning tunneling microscope. The effective quenching suppression and nanocavity plasmonic enhancement allow us to achieve intense and stable single-molecule electroluminescence. Second-order photon correlation measurements reveal an evident photon antibunching dip with the single-photon purity down to g (2)(0) = 0.09, unambiguously confirming the single-photon emission nature of the single-molecule electroluminescence. Furthermore, we demonstrate an ultrahigh-density array of identical single-photon emitters.Molecular emitters offer a promising solution for single-photon generation. Here, by exploiting electronic decoupling by an ultrathin dielectric spacer and emission enhancement by a resonant plasmonic nanocavity, the authors demonstrate electrically driven single-photon emission from a single molecule.

Interaction between Corneal and Internal Ocular Aberrations Induced by Orthokeratology and Its Influential Factors.

PURPOSE: To investigate the interaction between corneal, internal, and total wavefront aberrations (WAs) and their influential factors during orthokeratology (OK) treatment in Chinese adolescents. METHODS: Thirty teenagers (n = 30 eyes) were enrolled in the study; spherical equivalent refraction (SE), corneal curvature radius (CCR), central corneal thickness (CCT), WAs, and the difference in limbal transverse diameter and OK lens diameter (ΔLLD) were detected before and after one-month OK treatment. Every component of WAs was measured simultaneously by iTrace aberrometer. The influential factors of OK-induced WAs were analyzed. RESULTS: SE and CCT decreased while CCR increased significantly (P < 0.01). Higher-order aberrations (HOAs), Spherical aberrations (SAs), and coma increased significantly (P < 0.01). Corneal horizontal coma (Z31-C) and corneal spherical aberrations (Z40-C) increased (P < 0.01). The HOAs, coma, SAs, Z31-C, Z31-T, Z40-C, and Z40-T were positively correlated with SE and CCR (P < 0.01). Z3-1-C showed negative correlations with (ΔLLD) and positive correlations with SE (P < 0.05). CONCLUSIONS: The increase in OK-induced HOAs is mainly attributed to Z31 and Z40 of cornea. Z3-1 in the internal component showed a compensative effect on the corneal vertical coma. The degree of myopic correction and increase in CCR may be the essential influential factors of the increase in Z31 and Z40. The appropriate size of the OK lens may be helpful to decrease OK-induced vertical coma.

Sub-nanometre control of the coherent interaction between a single molecule and a plasmonic nanocavity.

The coherent interaction between quantum emitters and photonic modes in cavities underlies many of the current strategies aiming at generating and controlling photonic quantum states. A plasmonic nanocavity provides a powerful solution for reducing the effective mode volumes down to nanometre scale, but spatial control at the atomic scale of the coupling with a single molecular emitter is challenging. Here we demonstrate sub-nanometre spatial control over the coherent coupling between a single molecule and a plasmonic nanocavity in close proximity by monitoring the evolution of Fano lineshapes and photonic Lamb shifts in tunnelling electron-induced luminescence spectra. The evolution of the Fano dips allows the determination of the effective interaction distance of ∼1 nm, coupling strengths reaching ∼15 meV and a giant self-interaction induced photonic Lamb shift of up to ∼3 meV. These results open new pathways to control quantum interference and field-matter interaction at the nanoscale.