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Macromolecular Rapid Communications Jun 2024Herein, fluorescent conducting tautomeric polymers (FCTPs) are developed by polymerizing 2-methylprop-2-enoic acid (MPEA), methyl-2-methylpropenoate (MMP),...
Herein, fluorescent conducting tautomeric polymers (FCTPs) are developed by polymerizing 2-methylprop-2-enoic acid (MPEA), methyl-2-methylpropenoate (MMP), N-(propan-2-yl)prop-2-enamide (PPE), and in situ-anchored 3-(N-(propan-2-yl)prop-2-enamido)-2-methylpropanoic acid (PPEMPA). Among as-synthesized FCTPs, the most promising characteristics in FCTP3 are confirmed by NMR and Fourier transform infrared (FTIR) spectroscopies, luminescence enhancements, and computational studies. In FCTP3, ─C(═O)NH─, -C(═O)N<, ─C(═O)OH, and ─C(═O)OCH3 subluminophores are identified by theoretical calculations and experimental analyses. These subluminophores facilitate redox characteristics, solid state emissions, aggregation-enhanced emissions (AEEs), excited-state intramolecular proton transfer (ESIPT), and conductivities in FCTP3. The ESIPT-associated dual emission/AEEs of FCTP3 are elucidated by time correlated single photon counting (TCSPC) investigation, solvent polarity effects, concentration-dependent emissions, dynamic light scattering (DLS) measurements, field emission scanning electron microscopy images, and computational calculations. The cyclic voltammetry measurements of FCTP3 indicate cumulative redox efficacy of ─C(═O)OH, ─C(═O)NH─/-C(═O)N<, ─C(─O─)═NH+─/─C(─O─)═N+, and ─C(═N)OH functionalities. In FCTP3, ESIPT-associated dual-emission enable in the selective detection of Cr(III)/Cu(II) at λ/λ with the limit of detection of 0.0343/0.079 ppb. The preferential interaction of Cr(III)/Cu(II) with FCTP3 (amide)/FCTP3 (imidol) and oxidation/reduction of Cr(III)/Cu(II) to Cr(VI)/Cu(I) are further supported by NMR-titration; FTIR and X-ray photoelectron spectroscopy analyses; TCSPC/electrochemical/DLS measurement; alongside theoretical calculations. The proton conductivity of FCTP3 is explored by electrochemical impedance spectroscopy and I-V measurements.
PubMed: 38950314
DOI: 10.1002/marc.202400363 -
ACS Applied Materials & Interfaces Jul 2024The photocatalytic conversion of solar energy to hydrogen is a promising pathway toward clean fuel production, yet it requires advancement to meet industrial-scale...
The photocatalytic conversion of solar energy to hydrogen is a promising pathway toward clean fuel production, yet it requires advancement to meet industrial-scale demands. This study demonstrates that the interface engineering of heterojunctions is a viable strategy to enhance the photocatalytic performance of CuInS/MoS. Specifically, CuInS nanoparticles are incorporated into MoS nanospheres via a wet impregnation technique to form an S-scheme heterojunction. This configuration facilitates directional electron transfer, optimizing electron utilization and fostering efficient photocatalytic processes. The presence of an S-scheme heterojunction in CuInS/MoS is corroborated by in situ irradiation X-ray photoelectron spectroscopy and density functional theory analyses, which confirm the directional movement of electrons at the interface of heterojunction. Comprehensive characterization of the heterojunction photocatalyst, including phase, structural, and photoelectric property assessments, reveals a significant specific surface area and light absorption capability. These attributes augment the number of active sites available in CuInS/MoS for proton reduction reactions. This study offers a pragmatic approach for designing metal sulfide-based photocatalysts via strategic interface engineering, potentially advancing the field toward sustainable hydrogen production.
PubMed: 38950183
DOI: 10.1021/acsami.4c05199 -
Health Physics Jul 2024We had previously developed a measurement method using an imaging plate (IP) to evaluate and address surface contamination caused by the release of radioactive materials...
We had previously developed a measurement method using an imaging plate (IP) to evaluate and address surface contamination caused by the release of radioactive materials during the Fukushima nuclear accident. The measurement units for the surface contamination density were in relative values [described as relative luminescence levels measured in luminescence arbitrary units (LAU)], but the evaluation was required in absolute values, such as Bq cm-2, to enable appropriate control of exposure doses. This study establishes a method for converting the IP measurements of surface contamination density due to environmental radioactivity into absolute values. Soil contaminated with radioactive materials from the Fukushima nuclear accident was collected to create a working reference material (WRM). The conversion coefficient for surface contamination density was calculated using the WRM values measured with an IP and high-purity germanium detectors. The IP measurement values were converted into the surface contamination density using the conversion coefficient. The WRM values measured with the IP and high-purity germanium detectors were 324.1 LAU and 32.22 ± 2.27 Bq cm-2, respectively. The surface contamination density conversion factor was calculated as 0.0994. The surface contamination density on the roof of the Tsukuba City facility was re-evaluated using the conversion factor. The average value of 29,972 Bq m-2 matched the amount of radioactive material fallen in Tsukuba City. By standardizing the measurement conditions for surface contamination when using IPs, we successfully quantified the surface contamination density with an accuracy comparable to that of conventional methods. This method is expected to make a significant contribution to efficient radiation safety management.
PubMed: 38949861
DOI: 10.1097/HP.0000000000001818 -
Angewandte Chemie (International Ed. in... Jul 2024The diterpene synthase AfAS was identified from Aspergillus fumigatiaffinis. Its amino acid sequence and - according to a structural model - active site architecture are...
The diterpene synthase AfAS was identified from Aspergillus fumigatiaffinis. Its amino acid sequence and - according to a structural model - active site architecture are highly similar to those of the fusicocca-2,10(14)-diene synthase PaFS, but AfAS produces a structurally much more complex diterpene with a novel 6-5-5-5 tetracyclic skeleton called asperfumene. The cyclisation mechanism of AfAS was elucidated through isotopic labelling experiments and DFT calculations. The reaction cascade proceeds in its initial steps through similar intermediates as for the PaFS cascade, but then diverges through an unusual vicinal deprotonation-reprotonation process that triggers a skeletal rearrangement at the entrance to the steps leading to the unique asperfumene skeleton. The structural model revealed only one major difference between the active sites: The PaFS residue F65 is substituted by I65 in AfAS. Intriguingly, site-directed mutagenesis experiments with both diterpene synthases revealed that position 65 serves as a bidirectional functional switch for the biosynthesis of tetracyclic asperfumene versus structurally less complex diterpenes.
PubMed: 38949843
DOI: 10.1002/anie.202407895 -
Chemical Communications (Cambridge,... Jul 2024The mechanism of oxidation of phenols by tetrahedral copper(II)-halide complexes was investigated to demonstrate that phenols with an electron-withdrawing substituent...
The mechanism of oxidation of phenols by tetrahedral copper(II)-halide complexes was investigated to demonstrate that phenols with an electron-withdrawing substituent are oxidized a proton-transfer/electron-transfer (PTET) mechanism, whereas phenols with an electron-donating substituent involve a concerted proton/electron transfer (CPET) mechanism. The importance of the tetrahedral geometry of the metal centre as well as the effects of the halide ligands of the substrates were explored.
PubMed: 38949670
DOI: 10.1039/d4cc02483d -
Medical Physics Jul 2024MR-integrated proton therapy is under development. It consists of the unique challenge of integrating a proton pencil beam scanning (PBS) beam line nozzle with an...
BACKGROUND
MR-integrated proton therapy is under development. It consists of the unique challenge of integrating a proton pencil beam scanning (PBS) beam line nozzle with an magnetic resonance imaging (MRI) scanner. The magnetic interaction between these two components is deemed high risk as the MR images can be degraded if there is cross-talk during beam delivery and image acquisition.
PURPOSE
To create and benchmark a self-consistent proton PBS nozzle model for empowering the next stages of MR-integrated proton therapy development, namely exploring and de-risking complete integrated prototype system designs including magnetic shielding of the PBS nozzle.
MATERIALS AND METHODS
Magnetic field (COMSOL ) and radiation transport (Geant4) models of a proton PBS nozzle located at OncoRay (Dresden, Germany) were developed according to the manufacturers specifications. Geant4 simulations of the PBS process were performed by using magnetic field data generated by the COMSOL simulations. In total 315 spots were simulated which consisted of a scan pattern with 5 cm spot spacings and for proton energies of 70, 100, 150, 200, and 220 MeV. Analysis of the simulated deflection at the beam isocenter plane was performed to determine the self-consistency of the model. The magnetic fringe field from a sub selection of 24 of the 315 spot simulations were directly compared with high precision magnetometer measurements. These focused on the maximum scanning setting of 20 cm beam deflection as generated from the second scanning magnet in the PBS for a proton beam energy of 220 MeV. Locations along the beam line central axis (CAX) were measured at beam isocenter and downstream of 22, 47, 72, 97, and 122 cm. Horizontal off-axis positions were measured at 22 cm downstream of isocenter ( 50, 100, and 150 cm from CAX).
RESULTS
The proton PBS simulations had good spatial agreement to the theoretical values in all 315 spots examined at the beam line isocenter plane (0-2.9 mm differences or within 1.5 % of the local spot deflection amount). Careful analysis of the experimental measurements were able to isolate the changes in magnetic fields due solely to the scanning magnet contribution, and showed 1.9 1.2 -9.4 1.2 changes over the range of measurement locations. Direct comparison with the equivalent simulations matched within the measurement apparatus and setup uncertainty in all but one measurement point.
CONCLUSIONS
For the first time a robust, accurate and self-consistent model of a proton PBS nozzle assembly has been created and successfully benchmarked for the purposes of advancing MR-integrated proton therapy research. The model will enable confidence in further simulation based work on fully integrated designs including MRI scanners and PBS nozzle magnetic shielding in order to de-risk and realize the full potential of MR-integrated proton therapy.
PubMed: 38949569
DOI: 10.1002/mp.17279 -
The Journal of Physical Chemistry. B Jul 2024Proton (H) motive force (PMF) serves as the energy source for the flagellar motor rotation, crucial for microbial motility. Here, to control PMF using light, we...
Proton (H) motive force (PMF) serves as the energy source for the flagellar motor rotation, crucial for microbial motility. Here, to control PMF using light, we introduced light-driven inward and outward proton pump rhodopsins, XeR and AR3, into . The motility of cells expressing XeR and AR3 significantly decreased and increased upon illumination, respectively. Tethered cell experiments revealed that, upon illumination, the torque of the flagellar motor decreased to nearly zero (28 pN nm) with XeR, while it increased to 1170 pN nm with AR3. These alterations in PMF correspond to +146 mV (XeR) and -140 mV (AR3), respectively. Thus, bidirectional optical control of PMF in was successfully achieved by using proton pump rhodopsins. This system holds a potential for enhancing our understanding of the roles of PMF in various biological functions.
PubMed: 38949422
DOI: 10.1021/acs.jpcb.4c03027 -
Physical Review Letters Jun 2024The LHCb Collaboration measures production of the exotic hadron χ_{c1}(3872) in proton-nucleus collisions for the first time. Comparison with the charmonium state...
The LHCb Collaboration measures production of the exotic hadron χ_{c1}(3872) in proton-nucleus collisions for the first time. Comparison with the charmonium state ψ(2S) suggests that the exotic χ_{c1}(3872) experiences different dynamics in the nuclear medium than conventional hadrons, and comparison with data from proton-proton collisions indicates that the presence of the nucleus may modify χ_{c1}(3872) production rates. This is the first measurement of the nuclear modification factor of an exotic hadron.
PubMed: 38949352
DOI: 10.1103/PhysRevLett.132.242301 -
Physical Review Letters Jun 2024A search is presented for baryon number violating interactions in top quark production and decay. The analysis uses data from proton-proton collisions at a...
A search is presented for baryon number violating interactions in top quark production and decay. The analysis uses data from proton-proton collisions at a center-of-mass energy of 13 TeV, collected with the CMS detector at the LHC with an integrated luminosity of 138 fb^{-1}. Candidate events are selected by requiring two oppositely charged leptons (electrons or muons) and exactly one jet identified as originating from a bottom quark. Multivariate discriminants are used to separate the signal from the background. No significant deviation from the standard model prediction is observed. Upper limits are placed on the strength of baryon number violating couplings. For the first time the production of single top quarks via baryon number violating interactions is studied. This allows the search to set the most stringent constraints to date on the branching fraction of the top quark decay to a lepton, an up-type quark (u or c), and a down-type quark (d, s, or b). The results improve the previous bounds by 3 to 6 orders of magnitude based on the fermion flavor combination of the baryon number violating interactions.
PubMed: 38949350
DOI: 10.1103/PhysRevLett.132.241802 -
Physical Review Letters Jun 2024We present a first search for dark-trident scattering in a neutrino beam using a dataset corresponding to 7.2×10^{20} protons on target taken with the MicroBooNE...
We present a first search for dark-trident scattering in a neutrino beam using a dataset corresponding to 7.2×10^{20} protons on target taken with the MicroBooNE detector at Fermilab. Proton interactions in the neutrino target at the main injector produce π^{0} and η mesons, which could decay into dark-matter (DM) particles mediated via a dark photon A^{'}. A convolutional neural network is trained to identify interactions of the DM particles in the liquid-argon time projection chamber (LArTPC) exploiting its imagelike reconstruction capability. In the absence of a DM signal, we provide limits at the 90% confidence level on the squared kinematic mixing parameter ϵ^{2} as a function of the dark-photon mass in the range 10≤M_{A^{'}}≤400 MeV. The limits cover previously unconstrained parameter space for the production of fermion or scalar DM particles χ for two benchmark models with mass ratios M_{χ}/M_{A^{'}}=0.6 and 2 and for dark fine-structure constants 0.1≤α_{D}≤1.
PubMed: 38949335
DOI: 10.1103/PhysRevLett.132.241801