Annihilator dimers enhance triplet fusion upconversion

Optical upconversion is a net process by which two low energy photons are converted into one higher energy photon. There is vast potential to exploit upconversion in applications ranging from solar energy and biological imaging to data storage and photocatalysis. Here, we link two upconverting chromophores together to synthesize a series of novel tetracene dimers for use as annihilators. When compared with the monomer annihilator, TIPS–tetracene, the dimers yield a strong enhancement in the triplet fusion process, also known as triplet–triplet annihilation, as demonstrated via a large increase in upconversion efficiency and an order of magnitude reduction of the threshold power for maximum yield. Along with the ongoing rapid improvements to sensitizer materials, the dimerization improvements demonstrated here open the way to a wide variety of emerging upconversion applications

Anthracene Diphosphate Ligands for CdSe Quantum Dots; Molecular Design for Efficient Upconversion

Quantum dot (QD)-sensitized photon upconversion follows a multi-step energy transfer process from the QD to transmitter ligand to a soluble annihilator. Using a novel 10-R-anthracene-1,8-diphosphoric acid (R = octyl, 2-hexyldecyl, phenyl) ligand with high binding affinity for CdSe QD surfaces, we demonstrate a photon upconversion process that is limited by the transmitter to annihilator transfer efficiency. Using 1H NMR spectroscopy, we demonstrate that these bidentate diphosphate ligands rapidly and irreversibly displace two carboxylate ligands. These ligands mediate energy transfer from the photoexcited QDs to a triplet annihilator (1,10-diphenylanthracene), producing overall photon upconversion quantum efficiencies as high as 17%, the highest for QDs with no shells. Transient absorption spectroscopy shows that the anthracene dihydrogen phosphate (ADP) ligand supports a 3.4 fold longer triplet state lifetime compared to 9-anthracene carboxylic acid (299.9 ± 9.5 vs 88.2 ± 2.1 μs), increasing the probability of energy transfer

Case Reports1. A Late Presentation of Loeys-Dietz Syndrome: Beware of TGFβ Receptor Mutations in Benign Joint Hypermobility

Background: Thoracic aortic aneurysms (TAA) and dissections are not uncommon causes of sudden death in young adults. Loeys-Dietz syndrome (LDS) is a rare, recently described, autosomal dominant, connective tissue disease characterized by aggressive arterial aneurysms, resulting from mutations in the transforming growth factor beta (TGFβ) receptor genes TGFBR1 and TGFBR2. Mean age at death is 26.1 years, most often due to aortic dissection. We report an unusually late presentation of LDS, diagnosed following elective surgery in a female with a long history of joint hypermobility. Methods: A 51-year-old Caucasian lady complained of chest pain and headache following a dural leak from spinal anaesthesia for an elective ankle arthroscopy. CT scan and echocardiography demonstrated a dilated aortic root and significant aortic regurgitation. MRA demonstrated aortic tortuosity, an infrarenal aortic aneurysm and aneurysms in the left renal and right internal mammary arteries. She underwent aortic root repair and aortic valve replacement. She had a background of long-standing joint pains secondary to hypermobility, easy bruising, unusual fracture susceptibility and mild bronchiectasis. She had one healthy child age 32, after which she suffered a uterine prolapse. Examination revealed mild Marfanoid features. Uvula, skin and ophthalmological examination was normal. Results: Fibrillin-1 testing for Marfan syndrome (MFS) was negative. Detection of a c.1270G > C (p.Gly424Arg) TGFBR2 mutation confirmed the diagnosis of LDS. Losartan was started for vascular protection. Conclusions: LDS is a severe inherited vasculopathy that usually presents in childhood. It is characterized by aortic root dilatation and ascending aneurysms. There is a higher risk of aortic dissection compared with MFS. Clinical features overlap with MFS and Ehlers Danlos syndrome Type IV, but differentiating dysmorphogenic features include ocular hypertelorism, bifid uvula and cleft palate. Echocardiography and MRA or CT scanning from head to pelvis is recommended to establish the extent of vascular involvement. Management involves early surgical intervention, including early valve-sparing aortic root replacement, genetic counselling and close monitoring in pregnancy. Despite being caused by loss of function mutations in either TGFβ receptor, paradoxical activation of TGFβ signalling is seen, suggesting that TGFβ antagonism may confer disease modifying effects similar to those observed in MFS. TGFβ antagonism can be achieved with angiotensin antagonists, such as Losartan, which is able to delay aortic aneurysm development in preclinical models and in patients with MFS. Our case emphasizes the importance of timely recognition of vasculopathy syndromes in patients with hypermobility and the need for early surgical intervention. It also highlights their heterogeneity and the potential for late presentation. Disclosures: The authors have declared no conflicts of interes

Halide mixing inhibits exciton transport in two-dimensional perovskites despite phase purity

Halide mixing is one of the most powerful techniques to tune the optical bandgap of metal-halide perovskites. However, halide mixing has commonly been observed to result in phase segregation, which reduces excited-state transport and limits device performance. While the current emphasis lies on the development of strategies to prevent phase segregation, it remains unclear how halide mixing may affect excited-state transport even if phase purity is maintained. Here, we study exciton transport in phase pure mixed-halide 2D perovskites of (PEA)2Pb(I1-xBrx)4. Using transient photoluminescence microscopy, we show that, despite phase purity, halide mixing inhibits exciton transport. We find a significant reduction even for relatively low alloying concentrations. By performing Brownian dynamics simulations, we are able to reproduce our experimental results and attribute the decrease in diffusivity to the energetically disordered potential landscape that arises due to the intrinsic random distribution of alloying sitesThis work has been supported by the Spanish Ministry of Economy and Competitiveness through the “Mari ́ a de Maeztu” Program for Units of Excellence in R&D (MDM-2014-0377). M.S. acknowledges the financial support through a Doc.Mobility Fellowship from the Swiss National Science Foundation (SNF) with grant number 187676. In addition, M.S. acknowledges the financial support of a fellowship from ”la Caixa” Foundation (ID 100010434). The fellowship code is LCF/BQ/IN17/11620040. Further, M.S. has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No. 713673. F.P. acknowledges support from the Spanish Ministry for Science, Innovation, and Universities through the state program (PGC2018-097236-A-I00) and through the Ramón y Cajal program (RYC-2017-23253), as well as the Comunidad de Madrid Talent Program for Experienced Researchers (2016-T1/IND-1209). M.M., N.C., and R.D.B. acknowledge support from the Spanish Ministry of Economy, Industry, and Competitiveness through Grant FIS2017-86007-C3-1-P (AEI/FEDER, EU). D.N.C. acknowledges the support of the Rowland Fellowship at the Rowland Institute at Harvard University and the Department of Electrical Engineering at Stanford University. M.K.G. acknowledges the support of National Science Foundation Track 1 EPSCoR funding under the grant no. 1757220. D.A.K. acknowledges the support of a Rowland Foundation Postdoctoral Fellowshi

Triplet Fusion Upconversion Nanocapsules for Volumetric 3D Printing

Two-photon photopolymerization delivers prints without support structures and minimizes layering artifacts in a broad range of materials. This volumetric printing approach scans a focused light source throughout the entire volume of a resin vat and takes advantage of the quadratic power dependence of two photon absorption to produce photopolymerization exclusively at the focal point. While this approach has advantages, the widespread adoption of two photon photopolymerization is hindered by the need for expensive ultrafast lasers and extremely slow print speeds. Here we present an analogous quadratic process, triplet-triplet-annihilation-driven 3D printing, that enables volumetric printing at a focal point driven by <4 milliwatt-power continuous wave excitation. To induce photopolymerization deep within a vat, the key advance is the nanoencapsulation of photon upconversion solution within a silica shell decorated with solubilizing polymer ligands. This scalable self-assembly approach allows for scatter-free nanocapsule dispersal in a variety of organic media without leaking the capsule contents. We further introduce an excitonic strategy to systematically control the upconversion threshold to support either monovoxel or parallelized printing schemes, printing at power densities multiple orders of magnitude lower than power densities required for two-photon-based 3D printing. The application of upconversion nanocapsules to volumetric 3D printing provides access to the benefits of volumetric printing without the current cost, power, and speed drawbacks. The materials demonstrated here open opportunities for other triplet fusion upconversion-controlled applications

Gelation Dynamics during Photo-Cross-Linking of Polymer Nanocomposite Hydrogels

Embedding nanomaterials into polymer hydrogels enables the design of functional materials with tailored chemical, mechanical, and optical properties. Nanocapsules that protect interior cargo and disperse readily through a polymeric matrix have drawn particular interest for their ability to integrate chemically incompatible systems and to further expand the parameter space for polymer nanocomposite hydrogels. The properties of polymer nanocomposite hydrogels depend on the material composition and processing route, which were explored systematically in this work. The gelation kinetics of network-forming polymer solutions with and without silica-coated nanocapsules bearing polyethylene glycol (PEG) surface ligands were investigated using in situ dynamic rheology measurements. Network-forming polymers comprised either 4-arm or 8-arm star PEG with terminal anthracene groups, which dimerize upon irradiation with ultraviolet (UV) light. The PEG-anthracene solutions exhibited rapid gel formation upon UV exposure (365 nm); gel formation was observed as a crossover from liquid-like to solid-like behavior during in situ small-amplitude oscillatory shear rheology. This crossover time was non-monotonic with polymer concentration. Far below the overlap concentration (c/c* ≪ 1), spatially separated PEG-anthracene molecules were subject to forming intramolecular loops over intermolecular cross-links, thereby slowing the gelation process. Near the polymer overlap concentration (c/c* ∼ 1), rapid gelation was attributed to the ideal proximity of anthracene end groups from neighboring polymer molecules. Above the overlap concentration (c/c* > 1), increased solution viscosities hindered molecular diffusion, thereby reducing the frequency of dimerization reactions. Adding nanocapsules to PEG-anthracene solutions resulted in faster gelation than nanocapsule-free PEG-anthracene solutions with equivalent effective polymer concentrations. The final elastic modulus of nanocomposite hydrogels increased with nanocapsule volume fraction, signifying synergistic mechanical reinforcement by nanocapsules despite not being cross-linked into the polymer network. Overall, these findings quantify the impact of nanocapsule addition on the gelation kinetics and mechanical properties of polymer nanocomposite hydrogels, which are promising materials for applications in optoelectronics, biotechnology, and additive manufacturing