Fast detection of liver fibrosis with collagen-binding single-nanometer iron oxide nanoparticles via T1-weighted MRI.

SNIO-CBP, a single-nanometer iron oxide (SNIO) nanoparticle functionalized with a type I collagen-binding peptide (CBP), was developed as a T1-weighted MRI contrast agent with only endogenous elements for fast and noninvasive detection of liver fibrosis. SNIO-CBP exhibits 6.7-fold higher relaxivity compared to a molecular gadolinium-based collagen-binding contrast agent CM-101 on a per CBP basis at 4.7 T. Unlike most iron oxide nanoparticles, SNIO-CBP exhibits fast elimination from the bloodstream with a 5.7 min half-life, high renal clearance, and low, transient liver enhancement in healthy mice. We show that a dose of SNIO-CBP that is 2.5-fold lower than that for CM-101 has comparable imaging efficacy in rapid (within 15 min following intravenous injection) detection of hepatotoxin-induced liver fibrosis using T1-weighted MRI in a carbon tetrachloride-induced mouse liver injury model. We further demonstrate the applicability of SNIO-CBP in detecting liver fibrosis in choline-deficient L-amino acid-defined high-fat diet mouse model of nonalcoholic steatohepatitis. These results provide a platform with potential for the development of high relaxivity, gadolinium-free molecular MRI probes for characterizing chronic liver disease.

Near-Unity Superradiant Emission from Delocalized Frenkel Excitons in a Two-Dimensional Supramolecular Assembly.

We demonstrate three general effective strategies to mitigate non-radiative losses in the superradiant emission from supramolecular assemblies. We focus on J-aggregates of 5,5',6,6'-tetrachloro-1,1'-diethyl-3,3'-di(4-sulfobutyl)-benzimidazolocarbocyanine (TDBC) and elucidate the nature of their nonradiative processes. We show that self-annealing at room temperature, photo-brightening, and the purification of the dye monomers all lead to substantial increases in emission quantum yields (QYs) and a concomitant lengthening of the emission lifetime, with purification of the monomers having the largest effect. We use structural and optical measurements to support a microscopic model that emphasizes the deleterious effects of a small number of impurity and defect sites that serve as non-radiative recombination centers. This understanding has yielded a room temperature molecular fluorophore in solution with an unprecedented combination of fast emissive lifetime and high QY. We obtain superradiant emission from J-aggregates of TDBC in solution at room temperature with a QY of 82% coupled with an emissive lifetime of 174 ps. This combination of high QY and fast lifetime at room temperature makes supramolecular assemblies of purified TDBC a model system for the study of fundamental superradiance phenomena. High QY J-aggregates are uniquely suited for the development of applications that require high speed and high brightness fluorophores such as devices for high speed optical communication.

One-Dimensional Highly-Confined CsPbBr3 Nanorods with Enhanced Stability: Synthesis and Spectroscopy.

One-dimensional (1D) colloidal lead halide perovskites (LHPs) have potential as quantum emitters. Their study, however, has been hampered by their previous instability, leaving a gap in our understanding of structure-property relationships in colloidal LHPs with anisotropic shapes. Here, we synthesize stable, highly-confined 1D CsPbBr3 nanorods (NRs) and demonstrate their structural details and photoluminescence (PL) properties at both the ensemble and single particle levels. Using amino-terminated copolymers, we are able to stabilize and characterize 1D CsPbBr3 NRs utilizing transmission electron microscopy (TEM) and small angle scattering (SAS). Scanning transmission electron microscopy reveals that these NRs possess structural defects, including twists and inhomogeneity. Solution-phase photon correlation spectroscopy shows low biexciton-to-exciton quantum yield ratios (QYBX/QYX) and broad spectral line widths dominated by homogeneous broadening.

Single-nanometer iron oxide nanoparticles as tissue-permeable MRI contrast agents.

Magnetic nanoparticles are robust contrast agents for MRI and often produce particularly strong signal changes per particle. Leveraging these effects to probe cellular- and molecular-level phenomena in tissue can, however, be hindered by the large sizes of typical nanoparticle contrast agents. To address this limitation, we introduce single-nanometer iron oxide (SNIO) particles that exhibit superparamagnetic properties in conjunction with hydrodynamic diameters comparable to small, highly diffusible imaging agents. These particles efficiently brighten the signal in T1-weighted MRI, producing per-molecule longitudinal relaxation enhancements over 10 times greater than conventional gadolinium-based contrast agents. We show that SNIOs permeate biological tissue effectively following injection into brain parenchyma or cerebrospinal fluid. We also demonstrate that SNIOs readily enter the brain following ultrasound-induced blood-brain barrier disruption, emulating the performance of a gadolinium agent and providing a basis for future biomedical applications. These results thus demonstrate a platform for MRI probe development that combines advantages of small-molecule imaging agents with the potency of nanoscale materials.

Author Correction: Non-invasive monitoring of chronic liver disease via near-infrared and shortwave-infrared imaging of endogenous lipofuscin.

A Correction to this paper has been published: https://doi.org/10.1038/s41551-020-0569-y.

Non-invasive monitoring of chronic liver disease via near-infrared and shortwave-infrared imaging of endogenous lipofuscin.

Monitoring the progression of non-alcoholic fatty liver disease is hindered by a lack of suitable non-invasive imaging methods. Here, we show that the endogenous pigment lipofuscin displays strong near-infrared and shortwave-infrared fluorescence when excited at 808 nm, enabling label-free imaging of liver injury in mice and the discrimination of pathological processes from normal liver processes with high specificity and sensitivity. We also show that the near-infrared and shortwave-infrared fluorescence of lipofuscin can be used to monitor the progression and regression of liver necroinflammation and fibrosis in mouse models of non-alcoholic fatty liver disease and advanced fibrosis, as well as to detect non-alcoholic steatohepatitis and cirrhosis in biopsied samples of human liver tissue.

Bluish-Green Cu(I) Dimers Chelated with Thiophene Ring-Introduced Diphosphine Ligands for Both Singlet and Triplet Harvesting in OLEDs.

Two new Cu(I) dimers chelated with thiophene ring-introduced diphosphine ligands [Cu(µ2-I)dppt1]2 and [Cu(µ2-I)dppt2]2 (dppt1 = 3,4-bis(diphenylphosphino)thiophene, dppt2 = 2,3-bis(diphenylphosphino)thiophene) have been prepared and studied in terms of photoluminescence and electroluminescence properties. Both dimers exhibited two independent radiative decay pathways, which are equilibrated thermally at room temperature: one is thermally activated delay fluorescence (TADF) via the first singlet excited state (S1) decay and the other is phosphorescence via the first triplet excited state (T1) decay. The dual emission mechanism for both singlet and triplet harvesting, as well as excellent photoluminescence properties such as bluish-green emission color (487 and 483 nm), short decay times (9.46 and 7.62 µs), and high photoluminescence quantum yields (69% and 86%) of the two Cu(I) dimers, implies their potential to be highly efficient emitter molecules for organic light emitting diode (OLED) applications. As a result, the optimized OLEDs with [Cu(µ2-I)dppt2]2 showed the highest efficiency, exhibiting a current efficiency up to 32.2 cd A-1, a peak brightness of 3.67 × 103 cd m-2, as well as a maximum external quantum efficiency of 14.5%.

Deep Blue Phosphorescent Organic Light-Emitting Diodes with CIEy Value of 0.11 and External Quantum Efficiency up to 22.5.

Organic light-emitting diodes (OLEDs) based on red and green phosphorescent iridium complexes are successfully commercialized in displays and solid-state lighting. However, blue ones still remain a challenge on account of their relatively dissatisfactory Commission International de L'Eclairage (CIE) coordinates and low efficiency. After analyzing the reported blue iridium complexes in the literature, a new deep-blue-emitting iridium complex with improved photoluminescence quantum yield is designed and synthesized. By rational screening host materials showing high triplet energy level in neat film as well as the OLED architecture to balance electron and hole recombination, highly efficient deep-blue-emission OLEDs with a CIE at (0.15, 0.11) and maximum external quantum efficiency (EQE) up to 22.5% are demonstrated. Based on the transition dipole moment vector measurement with a variable-angle spectroscopic ellipsometry method, the ultrahigh EQE is assigned to a preferred horizontal dipole orientation of the iridium complex in doped film, which is beneficial for light extraction from the OLEDs.