A Multielectron and High-Potential Spirobifluorene-Based Posolyte for Aqueous Redox Flow Batteries.

The rising energy demand driven by human activity has posed pressing challenges in embracing renewable energy, necessitating advances in energy storage technologies to maximize their utilization efficiency. Recent studies in aqueous organic redox flow batteries have focused primarily on the development of organic negative electrolytes, while the progress in organic positive electrolytes remains constrained by limitations in their redox potentials and effective electron concentrations. Herein, we report a spatially twisted chlorinated spirobifluorene ammonium salts (CSFAs), created through an unexpected green chlorination-protection pathway during the initial cycling in the flow battery cell, utilizing chloride ions from counterions in aqueous solution. The chlorinated, nonplanar spiral structure of CSFAs possesses a one-step four-electron transfer electrochemical property and offers exceptional resistance to nucleophilic attacks, exhibiting an unprecedented redox potential as high as 1.05 V (vs. SHE). A full redox flow battery based on CSFA-Cl (chloride ions as the counter ions) with 1.4 M electron concentration achieved an average coulombic efficiency exceeding 99.4 % and a capacity utilization reaching 95 % of the four-electron capacity for a stable cycling over 250 cycles (~22 days). The present work exemplifies the use of side reactions to develop new redox species, which can be extended to create more structurally versatile energy storage materials.

A Long-Lived Water-Soluble Phenazine Radical Cation.

Long-lived water-soluble organic radical species have long been desired for applications in bioimaging and aqueous energy storage technologies. In the present work, we report a phenazine radical cation sodium 3,3'-(phenazine-5,10-diyl)bis(propane-1-sulfonate) (PSPR) with a high solubility of 1.4 M and high stability in water. Collaboratively demonstrated by experiments and theoretical calculations, PSPR is not prone to undergo dimerization or disproportionation reactions, and its appropriate electron density avoids reactions with oxygen or water, which contribute together to its long lifetime in water under air. With an open-shell configuration, PSPR shows interesting magnetic activity with a narrow linewidth in the electron paramagnetic resonance spectra and a magnetic circular dichroism response. PSPR exhibits an ambipolar redox activity in water. By pairing with a cheap zinc negative electrolyte, a high-performance aqueous organic redox flow battery based on PSPR as a positive electrolyte with an open-circuit voltage of 1.0 V is established, which shows no obvious capacity fade after cycling for 2500 cycles (∼27 days), demonstrating the great promise of PSPR for large-scale energy-storage technology.

Electrolyte Lifetime in Aqueous Organic Redox Flow Batteries: A Critical Review.

Aqueous organic redox flow batteries (RFBs) could enable widespread integration of renewable energy, but only if costs are sufficiently low. Because the levelized cost of storage for an RFB is a function of electrolyte lifetime, understanding and improving the chemical stability of active reactants in RFBs is a critical research challenge. We review known or hypothesized molecular decomposition mechanisms for all five classes of aqueous redox-active organics and organometallics for which cycling lifetime results have been reported: quinones, viologens, aza-aromatics, iron coordination complexes, and nitroxide radicals. We collect, analyze, and compare capacity fade rates from all aqueous organic electrolytes that have been utilized in the capacity-limiting side of flow or hybrid flow/nonflow cells, noting also their redox potentials and demonstrated concentrations of transferrable electrons. We categorize capacity fade rates as being "high" (>1%/day), "moderate" (0.1-1%/day), "low" (0.02-0.1%/day), and "extremely low" (≤0.02%/day) and discuss the degree to which the fade rates have been linked to decomposition mechanisms. Capacity fade is observed to be time-denominated rather than cycle-denominated, with a temporal rate that can depend on molecular concentrations and electrolyte state of charge through, e.g., bimolecular decomposition mechanisms. We then review measurement methods for capacity fade rate and find that simple galvanostatic charge-discharge cycling is inadequate for assessing capacity fade when fade rates are low or extremely low and recommend refining methods to include potential holds for accurately assessing molecular lifetimes under such circumstances. We consider separately symmetric cell cycling results, the interpretation of which is simplified by the absence of a different counter-electrolyte. We point out the chemistries with low or extremely low established fade rates that also exhibit open circuit potentials of 1.0 V or higher and transferrable electron concentrations of 1.0 M or higher, which are promising performance characteristics for RFB commercialization. We point out important directions for future research.

A simulation system of radiation field and its detection for nuclear and radiological emergency preparedness and response training.

Appropriate training of the related personnel is one of the most important aspects in nuclear and radiological emergency preparedness and response. The use of simulation training could provide the trainees learning experience of a lifelike, hands-on scenario without associated radiation safety restrictions. In this study, we established a radiation field simulation system that includes two separate parts. For small-area radiation field simulation, a set of simulation sources and detectors was designed based on ultra wide band distance measurement technology. For large-area field simulation, a Gaussian plume model was used to simulate the dispersion of released radioactive aerosols and calculate the consequent radiation field. Also, a Global Position System positioning and wireless transmission technique was used for simulation instruments' data acquisition. This system could create a verisimilar but also safe and radiation-free environment and can be used in the training of nuclear emergency first responders, rescue teams or radiation protection personnel.

Biomimetic Amino Acid Functionalized Phenazine Flow Batteries with Long Lifetime at Near-Neutral pH.

Aqueous organic redox flow batteries (AORFBs) are a promising electrochemical technology for large-scale energy storage. We report a biomimetic, ultra-stable AORFB utilizing an amino acid functionalized phenazine (AFP). A series of AFPs with various commercial amino acids at different substituted positions were synthesized and studied. 1,6-AFPs display much higher stability during cycling when compared to 2,7- and 1,8-AFPs. Mechanism investigations reveal that the reduced 2,7- and 1,8-AFPs tend to tautomerize and lose their reversible redox activities, while 1,6-AFPs possess ultra-high stability both in their oxidized and reduced states. By pairing 3,3'-(phenazine-1,6-diylbis(azanediyl))dipropionic acid (1,6-DPAP) with ferrocyanide at pH 8 with 1.0 M electron concentration, this flow battery exhibits an OCV of 1.15 V and an extremely low capacity fade rate of 0.5 % per year. These results show the importance of molecular engineering of redox-active organics for robust redox-flow batteries.

Copper-mediated trifluoromethylation of propargyl acetates leading to trifluoromethyl-allenes.

A copper-mediated trifluoromethylation of propargyl acetates with S-(trifluoromethyl)diphenylsulfonium triflate leading to trifluoromethylated allenes in moderate to excellent yields is described.

Skeletal dosimetry in a microCT image-based rat model for external photon irradiation.

Human skeletal dosimetry has experienced great developments in radiation protection in recent years by using the heterogeneous skeletal model. While for the rats experimentally used in radiation medicine, the investigation on skeletal dosimetry were mainly based on the homogeneous skeletal model, leading to inaccurate assessments of dose to radiosensitive tissues of red bone marrow (RBM) and bone surface. The purpose of this study is to develop a rat model with heterogeneous skeletal system and to investigate the dose difference in bone tissues for external photon irradiation. The high resolution of microCT images of a rat weighing 335 g were segmented into bone cortical, bone trabecular, bone marrow as well as other organs to construct the rat model. The absorbed dose to bone cortical, bone trabecular and bone marrow were calculated respectively by using Monte Carlo simulation for 22 external monoenergetic photon beams between 10 keV and 10 MeV under four different irradiation geometries conditions (left lateral [LL], right lateral [RL], dorsal-ventral [DV], ventral-dorsal [VD]). The calculated absorbed dose data were expressed as dose conversion coefficients and presented in this article, and the effect of irradiation conditions, photon energies and bone tissues density on the skeletal dose was discussed. The results showed that the dose conversion coefficients varying the photon energy for bone cortical, bone trabecular and bone marrow exhibit different trends and have the same sensitivity to irradiation conditions. The dose difference in bone tissues indicated that bone cortical and bone trabecular have significant attenuation effect on the energy deposition in bone marrow and bone surface for photon energies below 0.2 MeV. The set of dose conversion coefficients in this work can be used to determine the absorbed dose to skeletal system for external photon irradiation and to supplement the rat skeletal dosimetry.

Long-term operation of cathode-enhanced ecological floating bed coupled with microbial electrochemical system for urban surface water remediation: From lab-scale research to engineering application.

Ecological floating bed coupled with microbial electrochemical system (ECOFB-MES) has great application potential in micro-polluted water remediation yet limited by low electron transfer efficiency on the microbial/electrode interface. Here, an innovative cathode-enhanced EOCFB-MES was constructed with nano-Fe3O4 modification and applied for in-situ remediation both at lab scale (6 L, 62-day operation) and demonstration scale (2300 m2, 1-year operation). The cathode-enhanced ECOFB-MES exhibited superior removal in TOC (81.43 ± 2.05%), TN (85.12% ± 1.46%) and TP (59.80 ± 2.27%), much better than those of original ECOFB-MES and anode-enhanced ECOFB-MES in the laboratory test. Meanwhile, cathode-enhanced ECOFB-MES boosted current output by 33% than that of original ECOFB-MES, which made a great contribution to the improvement of ectopic electronic compensation for pollutant decontamination. Notably, cathode-enhanced ECOFB-MES presented high efficiency, stability and durability in the demonstration test, and fulfilled the average concentration of COD (9.5 ± 2.81 mg/L), TN (1.00 ± 0.21 mg/L) and TP (0.10 ± 0.04 mg/L) of effluent water to meet the Grade III (GB 3838-2002) with stable operation stage. Based on the KOSIM calculation, the removal loads of cathode-enhanced ECOFB-MES in carbon, nitrogen and phosphorus could reach 37.14 g COD/(d·m2), 2.62 g TN/(d·m2) and 0.55 g TP/(d·m2), respectively. According to the analysis of microbial communities and functional genes, the cathode modified by Fe3O4 made a sensible enrichment in electroactive bacteria (EAB) and nitrogen-converting bacteria (NCB) as well as facilitated the functional genes expression in electron transfer and nitrogen metabolism, resulting in the synergistic removal of carbon in sediment and nitrite in water. This study provided a brandnew technique reference for in-situ remediation of surface water in practical application.

Elucidation of interactions between myofibrillar proteins and κ-carrageenan as mediated by NaCl level: Perspectives on multiple spectroscopy and molecular docking.

The present study was aimed to investigate the intermolecular interaction between myofibrillar proteins (MP) and κ-carrageenan (KC) as mediated by KC concentration (0.1, 0.2, 0.3, and 0.4 %, w/w) and NaCl levels (0.3 and 0.6 M) based on the multiple spectroscopy and molecular docking. The results showed that the incorporation of KC increased the turbidity, zeta-potential, and surface hydrophobicity of MP-KC mixed sols with a dose-dependent manner, as well as significantly decreasing the protein solubility (P < 0.05), which indicated that the interaction between KC and MP promoted the expansion of protein structure and exposed more hydrophobic groups. Fluorescence spectra result revealed that the interaction between MP and KC was a static quenching in the fluorescence quenching process, which affected the aromatic amino acids residue microenvironment of MP. Moreover, the existence of KC decreased the α-helix contents of MP (P < 0.05), contributing to the transformation from random structure to organized configuration of MP. In addition, molecular forces, the molecular docking and thermodynamic parameters indicated that hydrophobic interactions, van der Waals force, and hydrogen bonding were considered as the main interaction forces between MP and KC. Furthermore, 0.6 M NaCl level rendered higher solubility and particle size, as well as lower turbidity and the surface hydrophobicity of MP-KC mixed sols than those with 0.3 M NaCl level (P < 0.05), which promoted the unfolding of MP molecule and subsequently increased the numbers of binding sites between MP and KC, facilitating the intermolecular interactions between MP and KC in mixed sols.

APPLICABILITY OF A HANDHELD LaBr3(Ce) SPECTROMETER FOR INTERNAL RADIOACTIVE CONTAMINATION EXAMINATION IN RADIOLOGICAL EMERGENCY.

In case of a nuclear or radiological emergency, there may be a very large population of individuals being affected by radiation exposure. Rapid and on-site examinations of possible internal radioactive contaminations are required for early dose assessment and large-scale screening. With the appropriate methodology, early dose information of internal exposure can be instantly obtained by a handheld spectrometer only. In this study, we extended the use of a handheld LaBr3 spectrometer to rough internal dose assessment. A family of real source BOMAB phantoms was applied for efficiency calibration of different detecting geometries. Detecting limits of several nuclides of major concern was also investigated. The result of this study can be used for initial dose assessment and medical triage during the first response of nuclear and radiological emergencies.

Study of rat organ dose conversion coefficients for external photon irradiation based on voxel model and Monte Carlo simulation.

A newly voxel rat model was developed from Micro-CT images of a rat to study rat organ dose for external photon irradiation. The voxel model with voxel size of 0.16 × 0.16 × 2 mm3 weighed about 323 g and contained most of the key organs or tissues. Monte Carlo N-particle code (MCNP) version 4C was utilized to calculate organ dose conversion coefficients for 21 external monoenergetic parallel photon beams between 10 keV and 10 MeV under four different irradiation geometries conditions (left lateral, right lateral, dorsal-ventral, ventral-dorsal). The calculated organ dose conversion coefficients were presented in tables and compared with published data based on a mouse model to investigate the effect of size and weight difference on organ dose. The calculated and comparison results show that the organ dose conversion for both mouse model and rat model exhibited similar energy dependence under the four ideal irradiation geometries, and the organ dose is sensitive to size and weight difference especially at photon energy below 0.1 MeV and above 2 MeV.

Study of new practical ESR dosimeter based on carbonated hydroxyapatite and its dosimetric properties.

The development of new dosimeters with good dosimetric properties is important for quality control in radiation applications. A new practical electron spin resonance (ESR) dosimeter based on carbonated hydroxyapatite that simulated the composition and structure of tooth enamel was specially synthesized. The synthesized material was investigated by transmission electron microscope, X-ray diffraction, fourier transform infrared spectroscopy and X-ray photo electron spectroscopy to confirm to the main composition of carbonated hydroxyapatite with CO32- successfully doped into the crystal lattice through optimizing the synthesis process of C/P molar ratio, pH value dynamical adjustment, annealing temperature and time. The dosimetric properties were systematically investigated by ESR spectroscopy. The results indicated that the radiation induced signal had a good dose response within a relatively wide dose range. The dose response was linear in the dose range of 0-400 Gy with a correlation coefficient of 0.9999 and had dose accumulative effect in the experimental dose range of 0-100 Gy. In a wider dose range up to 30 kGy, the dose response also presented linear feature in double-logarithmic coordinate system with a correlation coefficient of 0.9970. The dose detection limit was about 0.34Gy with a given probability of 95% confidence level depending upon a rigid calculation algorithm. The signal was extremely stable in the observation time of 360 days with a variation coefficient of 3.8%. The radiation sensitivity of the material showed no remarkable variation against photon energy from 662 KeV to 1.25 MeV and dose rate from 0.86 Gy/min to 12.17 Gy/min. The material showed more sensitive in lower photon energy range below 662 keV, which hint additional calibration may need when using in special photon energy condition. The preliminary results suggested that this newly developed dosimeter was potential to become a practical dosimeter that would expand the application fields of ESR dosimetry.

Efficient and stable single-doped white OLEDs using a palladium-based phosphorescent excimer.

A tetradentate Pd(ii) complex, Pd3O3, which exhibits highly efficient excimer emission is synthesized and characterized. Pd3O3 can achieve blue emission despite using phenyl-pyridine emissive ligands which have been a mainstay of stable green and red phosphorescent emitter designs, making Pd3O3 a good candidate for stable blue or white OLEDs. Pd3O3 exhibits strong and efficient phosphorescent excimer emission expanding the excimer based white OLEDs beyond the sole class of Pt complexes. Devices of Pd3O3 demonstrate peak external quantum efficiencies as high as 24.2% and power efficiencies of 67.9 Lm per W for warm white devices. Furthermore, Pd3O3 devices in a carefully designed stable structure achieved a device operational lifetime of nearly 3000 h at 1000 cd m-2 without any outcoupling enhancement while simultaneously achieving peak external quantum efficiencies of 27.3% and power efficiencies over 81 Lm per W.

EXPERIMENTAL STUDY ON ASSESSING INTERNAL RADIOACTIVE CONTAMINANTS BY USE OF NASAL SWAB.

Nasal swab analysis is an effective method to provide valuable information for early and fast estimates of alpha radionuclide intakes and resultant doses. In this study, an inhalation environment was built by use of lead nitrate aerosol to simulate alpha radioactive aerosol inhalation. The result of exposure and swabbing experiments with guinea pigs shows that the lead smeared on nasal swabs represents ∼13 % of intake if samples are acquired within 90 min after exposure and declines over time with a half-time of 1.4 h. The results also indicate a decreasing swabbing efficiency with post-exposure time. This study could provide useful information for the method of nasal swab used in nuclear and radiological emergencies.

Cu-Catalyzed C-H Trifluoromethylation of 3-Arylprop-1-ynes for the Selective Construction of Allenic Csp(2)-CF3 and Propargyl Csp(3)-CF3 Bonds.

A new method has been developed for the Cu-catalyzed C-H trifluoromethylation of 3-arylprop-1-ynes for the selective construction of allenic Csp(2)-CF3 and propargyl Csp(3)-CF3 bonds. The selective formation of allenic Csp(2)-CF3 and propargyl Csp(3)-CF3 bonds can be controlled by modifying the reaction conditions.

Aqueous colloid flow batteries with nano Prussian blue.

Flow battery is a safe and scalable energy storage technology in effectively utilizing clean power and mitigating carbon emissions from fossil fuel consumption. In the present work, we demonstrate an aqueous colloid flow battery (ACFB) with well-dispersed colloids based on nano-sized Prussian blue (PB) cubes, aiming at expanding the chosen area of various nano redox materials and lowering the cost of chemicals. Taking advantage of the two redox pairs of PB, the developed all-PB cell employing a low-cost dialysis membrane with the synthesized PB on both sides displays an open-circuit voltage (OCV) of 0.74 V. Moreover, when paired with an organic tetra pyridine macrocycle the cell with PB as positive electrolyte exhibits an OCV of 1.33 V and a capacity fade rate of 0.039 %/cycle (0.8 %/day). Redox-active colloids exhibit enduring physicochemical stability, with no evident structural or morphological changes after extensive cycling, highlighting their potential for cost-effective and reliable ACFB energy storage.