Structure and Function of a Dual Reductase?Dehydratase Enzyme System Involved in p-Terphenyl Biosynt
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Clinger, Jonathan A.↗
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High sensitivity pressure and temperature quantum sensing in pentacene-doped p-terphenyl single crystals
Quantum sensors’ responsiveness to their physical environment enables detection of variables such as temperature (T), pressure (P), and strain. We present a molecular platform for PT sensing using para-terphenyl crystals doped with pentacene (PDP), leveraging optically detected magnetic resonance (ODMR) of photoexcited triplet electron spins. We observe maximal frequency variations of df/dP=1.8 MHz/bar from 0-8 bar and df/dT=247 kHz/K from 79–330 K, over 1200 times and threefold greater, respectively, than those seen with nitrogen-vacancy centers in diamond and > 85-fold greater pressure sensitivity over the previous record. Density functional theory calculations indicate picometer-level PT-induced molecular orbital shifts are measurable via ODMR. PDP offers additional advantages including high sensor doping levels, narrow ODMR linewidths, high contrast, and low-cost single crystal growth. Overall, this work reports low-cost, optically-interrogated PT sensors and lays the foundation for increased versatility of quantum sensors through synthetic molecular design.
Magnetic properties and materials↗
A position and pulse shape discriminant p -terphenyl detector module
We present the development of a neutron detector array module made with para-terphenyl, a bright, fast, n/γ discriminating crystalline organic scintillator. The module is comprised of 2 cm × 2 cm × 2 cm p-terphenyl crystals that have been optically coupled together to create a pseudo-bar module. While only relying on two photo detectors, the module is capable of distinguishing interactions between up to eight crystals. Furthermore, the module retains the p-terphenyl’s pulse shape discrimination (PSD) capability. Together this makes the pseudo-bar module a promising position-sensitive neutron detector. Here we present characteristics of the pseudo-bar module - its timing resolution as well as its pulse shape and position discrimination capabilities, and briefly discuss future plans for utilizing an array of pseudo-bar modules in a useful neutron detector system.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Comparative analysis of new crystal and plastic scintillators for fast and thermal neutron detection
This paper considers scintillation and physical properties of efficient organic scintillators tested as single crystals and as components of plastics with pulse shape discrimination (PSD). For the first time, single crystals of 9,9-dimethyl-2-phenyl-9H-fluorene (PhF) were grown for studies of the basic scintillation properties of this new compound. Comparison to classical organic crystals, like anthracene, trans-stilbene, and p-terphenyl, and to more recently introduced organic glass showed that the new crystal belongs to a group of the most efficient scintillators, with light output exceeding that of trans-stilbene and PSD comparable to that of p-terphenyl. Furthermore, additional studies were conducted to evaluate scintillation performance and physical properties, like hardness and dye leaching, of plastic scintillators prepared with PhF, organic glass, and liquid diisopropylnaphthalene (DIPN) that were considered as examples for potential replacement of PPO (2,5-diphenyloxazole) in current commercial PSD plastic scintillators. Comparison of the highest performing plastic scintillators prepared with these dyes shows that PhF formulations produced a record light output (LO) increase of 69 % relative to EJ-200. Similar improvements obtained with 6 Li-loaded formulations showed that future development of PSD plastics should not be limited to use of PPO but must involve the search and exploration of new efficient dyes that may lead to discovery of much brighter organic scintillators with improved physical properties required for fast and thermal neutron detection, fast neutron spectroscopy, and antineutrino detection applications.
9,9-dimethyl-2-phenyl-9H-fluorene↗
Design of non-fluorinated proton exchange membranes from Poly(Terphenyl fluorenyl isatin) with fluorene-linked sulfonate groups and microblock structures
Proton exchange membranes (PEMs) are essential components in energy storage and conversion devices, such as fuel cells and electrolyzers. Here, in this study, we developed a series of non-fluorinated PEMs from poly(terphenyl fluorenyl isatin) with fluorene-pendent disulfonate groups. These polymers feature a microblock structure composed of hydrophobic blocks, hydrophilic blocks, and alternating blocks, arising from the differences in reactivity, concentration, and solubility between the hydrophobic p-terphenyl and hydrophilic disulfonated fluorene monomers. As a result, the sulfonic acid groups are unevenly distributed along the polymer chains, forming densely charged regions (IEC = 3.52 meq/g) with large ion clusters and lightly charged regions (IEC = 2.16 meq/g) with small ion clusters. This microstructure, combined with the degree of sulfonation, significantly influences the overall properties of the membranes, including robust mechanical strength (47.1–63.2 MPa), high thermal stability (up to 270 °C), low swelling ratio (18–25% at 80 °C), and high proton conductivity (136–169 mS/cm in deionized water at 80 °C). The PFLSH60 membrane demonstrated comparable fuel cell performance to Nafion 212. Its hydrogen crossover current density was more than two times lower (0.86 mA/cm 2 for PFLSH60 compared to 1.83 mA/cm 2 for Nafion 212) under testing conditions of 80 °C and 100% RH. This significantly reduced crossover improves fuel utilization in fuel cell stacks. This work offers valuable insights into the design of robust, high-performance PEMs by systematically analyzing the relationships between membrane structure, properties, and performance.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Electrochemically Mediated Au–C(sp 2 ) Anchors for Molecular Electronics
Terminal anchor groups play a key role in the stability and electronic properties of molecular junctions. Single molecule junctions typically consist of two preinstalled terminal anchors linking organic molecules to metal electrodes. Here, in this work, we show that p -terphenyl derivatives containing only a single terminal anchor show conductance features similar to junctions with two preinstalled terminal anchors. A set of p -terphenyl derivatives with one terminal anchor was prepared using automated chemical synthesis and characterized using single molecule electronics experiments, molecular dynamics (MD) simulations, bulk electrochemistry and spectroscopy, and nonequilibrium Green’s function-density functional theory (NEGF-DFT) calculations. Our results show that 4-amino- p -terphenyl (PPP) and related analogs exhibit a well-defined high conductance state that is diminished or absent in other p-terphenyl derivatives lacking a preinstalled amine terminal anchor or fluorine or methyl substitutions at the terminal para position. However, a low conductance state is observed in all amino- p -terphenyl derivatives with one preinstalled anchor due to molecular junctions formed by noncovalent dimeric π–π stacking interactions. The observed high conductance state diminishes upon the addition of reducing agents and is restored upon the addition of an oxidizing agent. Our results suggest that the high conductance state arises due to Au–C(sp 2 ) bond formation facilitated by a single electron oxidation event at the electrode surface. A series of control experiments with different anchor groups shows that primary amines play a key role in forming Au–C bonds for molecular junctions. Overall, these results suggest that Au–C bond formation gives rise to high conductance pathways in organic molecules containing only one preinstalled terminal anchor. Insights from this work can be leveraged in the design of molecular electronic devices, particularly in understanding the mechanisms of molecular binding and junction formation.
charge transport↗
Some characteristics of powder silica counters
Following the original idea of Peters, techniques have been developed to fabricate large area powder silica counters with refractive index between 1.06 to 1.12 in thicknesses of 1 cm and 2 cm respectively. The maximum size counter is 25 cm x 25 cm but the technique can be easily extended to 40 cm x 30 cm counters. Techniques have also been developed to dope this counter with the wavelength shifter p-terphenyl uniformly. The results of test runs at the Brookhaven National Laboratory and of laboratory runs using a superconducting magnet spectrometer on their performance are reported.
Badhwar, G. D.↗
UV lidar measurements of the stratospheric aerosol layer and comparison with other optical data
After the violent volcanic eruptions of El Chichon in Mexico (17.33 deg. N, 93.20 deg. W) in late March and early April 1982, enhanced stratospheric aerosols have been monitored by ruby (lasing wavelength lambda=694.3 nm) or Nd:YAG lidars (lambda=1064 or 532 nm). By these lidars, visible or near-infrared optical informations of stratospheric aerosols and their space-time variations can be obtained. It is usually difficult to measure the background level of stratospheric aerosols by an ultraviolet (UV) lidar, since Rayleigh scattering prevails over Mie scattering in the stratosphere. However, after the large volcanic eruptions, UV lidar measurements of stratospheric aerosols are possible. In order to obtain UV optical properties of stratospheric aerosols, measurements have been made at Fukuoka (33.65 deg. N, 130.35 deg. E) by a p-terphenyl dye laser at a wavelength of 340.5 nm. Observational results during October 1982, through May 1983, are shown and are compared with the results obtained by a ruby lidar at Tsukuba (36.05 deg. N, 140.13 deg. E).
Uchino, O.↗