Merging of Azulene and Perylene Diimide for Optical pH Sensors

Polycyclic aromatic hydrocarbons (PAHs) have emerged as promising materials for organic electronics, including organic photovoltaics (OPVs), organic field-effect transistors (OFETs), and organic light-emitting diodes (OLEDs). Particularly, non-hexagonal ring-fused PAHs are highly desirable due to their unique optoelectronic properties. Herein, a new redox-active azulene-perylene diimide triad 1 and its ring-fused counterpart, diazulenocoronene diimide 2, were synthesized and fully characterized by a combination of NMR, cyclic voltammetry, and UV-visible absorption spectroscopy. Direct comparison of their electronic properties leads us to the conclusion that a significant change in the localization of HOMO and LUMO occurs upon the fusion of azulene and perylene diimide in 2, leading to the lack of intramolecular charge-transfer character for transitions in the visible spectral region. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed to gain further insight into various electronic transitions. Moreover, we found that the adaptive response to acids and bases manifests itself in a reversible two-color change that can be attributed to changes in the chemical structures. Our findings pave the way for manipulating the relative HOMO and LUMO energy levels of organic chromophores by fusing non-alternant azulenes to an otherwise flat PAH, which could possibly lead to applications in organic electronics and optical sensors

Seagrass Health Modeling and Prediction with NASA Science Data

Previous research has demonstrated that MODIS data products can be used as inputs into the seagrass productivity model developed by Fong and Harwell (1994). To further explore this use to predict seagrass productivity, Moderate Resolution Imaging Spectroradiometer (MODIS) custom data products, including Sea Surface Temperature, Light Attenuation, and Chlorophyll-a have been created for use as model parameter inputs. Coastal researchers can use these MODIS data products and model results in conjunction with historical and daily assessment of seagrass conditions to assess variables that affect the productivity of the seagrass beds. Current monitoring practices involve manual data collection (typically on a quarterly basis) and the data is often insufficient for evaluating the dynamic events that influence seagrass beds. As part of a NASA-funded research grant, the University of Mississippi, is working with researchers at NASA and Radiance Technologies to develop methods to deliver MODIS derived model output for the northern Gulf of Mexico (GOM) to coastal and environmental managers. The result of the project will be a data portal that provides access to MODIS data products and model results from the past 5 years, that includes an automated process to incorporate new data as it becomes available. All model parameters and final output will be available through the use National Oceanic and Atmospheric Administration?s (NOAA) Environmental Research Divisions Data Access Program (ERDDAP) tools as well as viewable using Thematic Realtime Environmental Distributed Data Services (THREDDS) and the Integrated Data Viewer (IDV). These tools provide the ability to create raster-based time sequences of model output and parameters as well as create graphs of model parameters versus time. This tool will provide researchers and coastal managers the ability to analyze the model inputs so that the factors influencing a change in seagrass productivity can be determined over time

Atomically Well-defined Nitrogen Doping in the Cross-plane Transport through Graphene Heterojunctions

The nitrogen doping of graphene leads to graphene heterojunctions with a tunable bandgap, suitable for electronics, electrochemical, and sensing applications. However, the microscopic nature and charge transport properties of atomic-level nitrogen-doped graphene are still unknown, mainly due to the multiple doping sites with topological diversities. In this work, we fabricated the atomically well-defined N-doped graphene heterojunctions and investigated the cross-plane transport through these heterojunctions to reveal the effects of doping on their electronic properties. We found that different doping number of nitrogen atoms leads to a conductance difference of up to ~288, and the conductance of graphene heterojunctions with nitrogen-doping at different positions in the conjugated framework can also lead to a conductance difference of ~170. Combined ultraviolet photoelectron spectroscopy measurements and theoretical calculations reveal that the insertion of nitrogen atoms into the conjugation framework significantly stabilizes the frontier molecular orbitals, leading to a change in the relative positions of HOMO and LUMO to the Fermi level of the electrodes. Our work provides a unique insight into the role of nitrogen doping on the charge transport through graphene heterojunctions and materials at the single atomic level

Strong signature of electron-vibration coupling in molecules on Ag(111) triggered by tip-gated discharging

Abstract Electron-vibration coupling is of critical importance for the development of molecular electronics, spintronics, and quantum technologies, as it affects transport properties and spin dynamics. The control over charge-state transitions and subsequent molecular vibrations using scanning tunneling microscopy typically requires the use of a decoupling layer. Here we show the vibronic excitations of tetrabromotetraazapyrene (TBTAP) molecules directly adsorbed on Ag(111) into an orientational glassy phase. The electron-deficient TBTAP is singly-occupied by an electron donated from the substrate, resulting in a spin 1/2 state, which is confirmed by a Kondo resonance. The TBTAP•− discharge is controlled by tip-gating and leads to a series of peaks in scanning tunneling spectroscopy. These occurrences are explained by combining a double-barrier tunneling junction with a Franck-Condon model including molecular vibrational modes. This work demonstrates that suitable precursor design enables gate-dependent vibrational excitations of molecules on a metal, thereby providing a method to investigate electron-vibration coupling in molecular assemblies without a decoupling layer

Flexible superlubricity unveiled in sidewinding motion of individual polymeric chains

A combination of low temperature atomic force microcopy and molecular dynamic simulations is used to demonstrate that soft designer molecules realize a sidewinding motion when dragged over a gold surface. Exploiting their longitudinal flexibility, pyrenylene chains are indeed able to lower diffusion energy barriers via on-surface directional locking and molecular strain. The resulting ultralow friction reaches values on the order of tens of pN reported so far only for rigid chains sliding on an incommensurate surface. Therefore, we demonstrate how molecular flexibility can be harnessed to realize complex nanomotion while retaining a superlubric character. This is in contrast with the paradigm guiding the design of most superlubric nanocontacts (mismatched rigid contacting surfaces

Gate-tunable topological superconductivity in a supramolecular electron spin lattice

Topological superconductivity emerges in chains or arrays of magnetic atoms coupled to a superconductor. However, the external controllability of such systems with gate voltages is detrimental for their future implementation in a topological quantum computer. Here we showcase the supramolecular assembly of radical molecules on Pb(111), whose discharge is controlled by the tip of a scanning tunneling microscope. Charged molecules carry a spin-1/2 state, as confirmed by observing Yu-Shiba-Rusinov in-gap states by tunneling spectroscopy at millikelvin temperature. Low energy modes are localized at island boundaries with a long decay towards the interior, whose spectral signature is consistent with Majorana zero modes protected by mirror symmetry. Our results open up a vast playground for the synthesis of gate-tunable organic topological superconductors

Repair of Parastomal Hernias with Biologic Grafts: A Systematic Review

Contains fulltext : 98303.pdf (publisher's version ) (Open Access)BACKGROUND: Biologic grafts are increasingly used instead of synthetic mesh for parastomal hernia repair due to concerns of synthetic mesh-related complications. This systematic review was designed to evaluate the use of these collagen-based scaffolds for the repair of parastomal hernias. METHODS: Studies were retrieved after searching the electronic databases MEDLINE, EMBASE and Cochrane CENTRAL. The search terms 'paracolostomy', 'paraileostomy', 'parastomal', 'colostomy', 'ileostomy', 'hernia', 'defect', 'closure', 'repair' and 'reconstruction' were used. Selection of studies and assessment of methodological quality were performed with a modified MINORS index. All reports on repair of parastomal hernias using a collagen-based biologic scaffold to reinforce or bridge the defect were included. Outcomes were recurrence rate, mortality and morbidity. RESULTS: Four retrospective studies with a combined enrolment of 57 patients were included. Recurrence occurred in 15.7% (95% confidence interval [CI] 7.8-25.9) of patients and wound-related complications in 26.2% (95% CI 14.7-39.5). No mortality or graft infections were reported. CONCLUSIONS: The use of reinforcing or bridging biologic grafts during parastomal hernia repair results in acceptable rates of recurrence and complications. However, given the similar rates of recurrence and complications achieved using synthetic mesh in this scenario, the evidence does not support use of biologic grafts

Effect of tert-butyl groups on electronic communication between redox units in tetrathiafulvalene-tetraazapyrene triads

The electronic effect of tert-butyl groups on intramolecular through-bond interactions between redox units in tetrathiafulvalene-tetraazapyrene (TAP) triads is investigated. The insertion of tert-butyl groups raises the TAP-localised LUMO level by 0.21 eV, in fairly good agreement with 0.17 eV determined by DFT calculations