Isomeric State Research Articles

Optically Controlled Recovery and Recycling of Homogeneous Organocatalysts Enabled by Photoswitches

AbstractWe address a critical challenge of recovering and recycling homogeneous organocatalysts by designing photoswitchable catalyst structures that display a reversible solubility change in response to light. Initially insoluble catalysts are UV‐switched to a soluble isomeric state, which catalyzes the reaction, then back‐isomerizes to the insoluble state upon completion of the reaction to be filtered and recycled. The molecular design principles that allow for the drastic solubility change over 10 times between the isomeric states, 87 % recovery by the light‐induced precipitation, and multiple rounds of catalyst recycling are revealed. This proof of concept will open up opportunities to develop highly recyclable homogeneous catalysts that are important for the synthesis of critical compounds in various industries, which is anticipated to significantly reduce environmental impact and costs.

Optically Controlled Recovery and Recycling of Homogeneous Organocatalysts Enabled by Photoswitches.

We address a critical challenge of recovering and recycling homogeneous organocatalysts by designing photoswitchable catalyst structures that display a reversible solubility change in response to light. Initially insoluble catalysts are UV-switched to a soluble isomeric state, which catalyzes the reaction, then back-isomerizes to the insoluble state upon completion of the reaction to be filtered and recycled. The molecular design principles that allow for the drastic solubility change over 10 times between the isomeric states, 87 % recovery by the light-induced precipitation, and multiple rounds of catalyst recycling are revealed. This proof of concept will open up opportunities to develop highly recyclable homogeneous catalysts that are important for the synthesis of critical compounds in various industries, which is anticipated to significantly reduce environmental impact and costs.

Probing the water hydrogen-bonding effects on the ground and low-lying excited states of phenanthroline isomers

In this work, the ground and low-lying excited states of a series of phenanthroline isomers (1,10-phenanthroline, 1,7-phenanthroline, and 4,7-phenanthroline) were investigated. Density functional theory (DFT) was used for determining the structural and energetic properties connected to the ground state (such as bond lengths and angles, hydrogen-bond interactions, vibrational frequencies, and relative energies) of each molecule while time-dependent DFT was employed for probing the excited state parameters (excitation energies, oscillator strengths, and structures); both approaches were used in combination with the CAM-B3LYP exchange–correlation functional and the cc-pVTZ basis set. The computations were performed in the gas-phase and water. The effects originating from the interactions with the solvent environment were examined by means of the integral equation formalism polarizable continuum model (IEF-PCM), as well as using a composite solvation model (CSM) through the incorporation of explicit water molecules in combination with IEF-PCM. In terms of relative stability, 1,10-phenanthroline became the most stable isomer when the combined implicit-explicit solvation was taken into account, an interesting behavior that may be assigned to the existence of a chain of hydrogen-bond interactions involving the two explicitly added water molecules and both nitrogen atoms from 1,10-phenanthroline. This feature provided better stabilization to the system when compared to the 1,7-phenanthroline and 4,7-phenanthroline. Taking the 1,10-phenanthroline isomer as an example, all its low-lying singlet excited states were determined to have non-zero oscillator strengths when the CSM was used and, more importantly, one among these states was found as being highly accessible (with oscillator strength = 0.9545). From the comparison with the results obtained using solely the implicit solvation (IEF-PCM results), it is possible to assign the presence of the hydrogen-bond interactions as being an important factor for making such excited state likely to be accessed.

Gas-phase electronic spectroscopy of nuclear spin isomer separated H2O@C60 + and D2O@C60 +

Gas-phase electronic spectra of HO@C and DO@C are presented. These data were obtained by one-photon dissociation of weakly bound helium complexes synthesised in a 3 K ion trap. Measurements were recorded in the vicinity of the electronic transitions of the C cage. Two-colour hole burning experiments enabled nuclear spin isomer pure data to be obtained. The spectra are rich in structure with many absorptions attributed to internal excitation of the encapsulated molecule accompanying the C electronic transition. The experimental data are complemented with density functional theory calculations using the B3LYP functional and 6-31++G** basis set.

Erratum: High-resolution, accurate multiple-reflection time-of-flight mass spectrometry for short-lived, exotic nuclei of a few events in their ground and low-lying isomeric states [Phys. Rev. C 99 , 064313 (2019)

Received 16 January 2023DOI:https://doi.org/10.1103/PhysRevC.107.029901Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasBeam diagnosticsBinding energy & massesIsomer decaysLifetimes & widthsNuclear bindingNuclear fragmentationNuclear reactionsNuclear structure & decaysSecondary beamsShell modelAccelerators & BeamsNuclear Physics

On the multipole mixing ratio of the 1066 keV transition from the 0.52 μs isomer of 180Hf

The nucleus 180Hf is one of the most primary examples of an axially symmetric prolate rotor. Combined with the presence of high-K isomers, spectroscopic studies can provide important information on the nature of its single-particle levels. Precise measurements are essential for constraining nuclear models and interpreting the nature of such isomeric states. In this work, the nucleus 180Hf was populated using the proton pick-up reaction 181Ta(11B,12C)180Hf at beam energy of 47 MeV at Horia Hulubei National Institute of Nuclear Physics and Engineering (IFIN-HH). The spin of the 1374 keV state and the mixing ratio of the 1066 keV transition have been measured, the latter with an increased precision compared to the previous value from literature. The presently measured spin of the 1374 keV state, currently assigned a tentative value of (41−), favors one of the two different values that were previously reported. The particular state constitutes the band-head of a rotational band in 180Hf. The measured multipolarity mixing ratio of the inter-band transition 1374→309 keV can provide important information for the testing and constraining of theoretical nuclear models used for the study of the intrinsic properties of 180Hf, as well as its neighboring isotopes.

Fundamentals of Rhenium-188 Radiopharmaceutical Chemistry.

The β- emitter, rhenium-188 (188Re), has long been recognized as an attractive candidate for targeted cancer radionuclide therapy (TRNT). This transition metal shares chemical similarities with its congener element technetium, whose nuclear isomer technetium-99m (99mTc) is the current workhorse of diagnostic nuclear medicine. The differences between these two elements have a significant impact on the radiolabelling methods and should always receive critical attention. This review aims to highlight what needs to be considered to design a successful radiopharmaceutical incorporating 118Re. Some of the most effective strategies for preparing therapeutic radiopharmaceuticals with 188Re are illustrated and rationalized using the concept of the inorganic functional group (core) and a simple ligand field theoretical model combined with a qualitative definition of frontiers orbitals. Of special interest are the Re(V) oxo and Re(V) nitrido functional groups. Suitable ligands for binding to these cores are discussed, successful clinical applications are summarized, and a prediction of viable future applications is presented. Rhenium-188 decays through the emission of a high energy beta particle (2.12 MeV max energy) and a half-life of 16.9 h. An ideal biological target would therefore be a high-capacity target site (transporters, potential gradients, tumour microenvironment) with less emphasis on saturable targets such as overexpressed receptors on smaller metastases.

Investigating the E2 nuclear resonance effect in kaonic atoms

The nuclear E2 resonance effect occurs when an atomic de-excitation energy is closely matched by a nuclear excitation energy. It produces an attenuation of some of the atomic X-ray lines in the resonant isotope target. Investigating the nuclear E2 resonance effect in kaonic atoms, important information about kaon-nucleus strong interaction can be provided. The only nuclear resonance effect was measured by G. L. Goldfrey, G- K. Lum and C. E. Wiegand at Lawrence Berkeley Laboratory, in 1975. The nuclear E2 resonance effect was observed in 25 hours of data taking, not enough to provide a conclusive result. In four kaonic Molybdenum isotopes (, , and ), the nuclear E2 resonance effect is expected at the same transition, with similar energy values. The KAMEO (Kaonic Atoms Measuring nuclear resonance Effects Observables) experiment plans to study the E2 nuclear resonance effect in kaonic Molybdenum isotopes at the DAΦNE e+e− collider, during the SIDDHARTA-2 experiment. The experimental strategy consists of exposing four solid strip targets, each enriched with one Molybdenum isotope, to negatively charged kaons, using a germanium detector for X-ray transition measurements. A further exposure of a non-resonant isotope solid strip target will be used as reference for standard non-resonant transitions.

Investigation of isomeric states in Rf255

Using the GABRIELA detector array, $\ensuremath{\gamma}$-ray and internal-conversion-electron decay spectroscopy has been performed on $^{255}\mathrm{Rf}$ nuclei that were produced via the $^{207}\mathrm{Pb}(^{50}\mathrm{Ti},2n)^{255}\mathrm{Rf}$ fusion-evaporation reaction using the SHELS velocity filter. Three isomers were identified in $^{255}\mathrm{Rf}$ with the aid of Geant4 simulations. The existence of two high-$K$ isomeric states in cascade has been confirmed. Possible three-quasiparticle configurations involving the coupling of the unpaired $9/{2}^{\ensuremath{-}}[734]$ neutron to two-quasiparticle states have been suggested and a likely decay scenario has been proposed on the basis of comparisons to Geant4 simulations. The simulations have also confirmed the existence of the $5/{2}^{+}[622]$ spin isomer at low excitation energy.

Facets of reaction mechanism in 6Li+181Ta system

More focused investigations are required to better understand the different modes of fusion phenomena in weakly bound projectiles. In order to comprehend the reaction mechanism of weakly bound projectiles, a new measurement of the evaporation residue cross sections from the 6Li-induced reaction on 181Ta in the 4.5–7.1 MeV/nucleon energy range has been reported in this article. The γ-ray spectrometry has been employed to identify the 183m,g Os, 182Os, 183Re, and 183,182m2,180Ta residues produced in the reaction via different evaporation channels. The EMPIRE-3.2.2 code, which houses both the equilibrium and pre-equilibrium models in its framework, and PACE4 have been tasked to analyze the measured excitation functions. Out of the two, EMPIRE-3.2.2 demonstrates better agreement with the data. A systematic analysis of the measured data and theoretical background indicates that the complete and incomplete fusion of 6Li contribute to the residual cross sections. Thus, the strength of the partial fusion has been inferred. Further, the neutron transfer channels have been found to contribute significantly to the reaction dynamics; hence they are investigated using the coupled reaction channel calculations and discussed in detail. The isomeric cross section ratio obtained from the measured residual cross sections of the isomeric pair of 183Os highlights the significance of angular momentum and relative spins of the ground and isomeric states as a function of projectile incident energy.

How to Use Nested Probes Coupling to Increase the Local NMR/MRI Resolution and Sensitivity for Specific Experiments

In this paper, we address resonant systems intended to be used with the commercial main resonator present on all NMR or MRI instruments. The purpose of this approach is to get an improvement regarding the spatial localization and signal to noise ratio provided by an additional smaller coil. Both coils are coupled to the same sample region, and thus, are inductively coupled through their common magnetic flux. The coupling strength is characterized by the so-called mutual inductance M. Two practical devices are presented. Firstly, a geometrical passive decoupled resonant system (M = 0) allows getting a sensitive received signal from the maximized nuclear macroscopic magnetization, excited by the main resonator and detected by the smaller sniffer coil. Secondly, a strongly coupled resonant system allows us to considerably locally improve the magnetic component of the RF near field to provide an efficient nuclear spin magnetization excitation and a high received signal. For both configurations, the behavior of the coils system regarding the amplitude of B1 is addressed. Finally, specific technical hints to achieve optimum energy transfer (impedance matching) are discussed, taking into account the non-ideal RF characteristics of the involved components. Examples of MRI experiments, as well as workbench evaluations and simulations support the principles exposed here.

Decay spectroscopy of Os171,172 and Ir171,172,174

We report on a study of the α-decay fine structure and the associated Eα−Eγ correlations in the decays of Os171,172 and Ir171,172,174. In total, 13 new α-decay energy lines have been resolved, and three new γ-ray transitions have been observed following the new decay branches to Re168 and W167. The weak α-decay branch from the bandhead of the νi13/2 band in Os171 observed in this work highlights an unusual competition between α, β, and electromagnetic decays from this isomeric state. The nucleus Os171 is therefore one of few nuclei observed to exhibit three different decay modes from the same excited state. The nuclei of interest were produced in Mo92(Kr83,xpyn) fusion-evaporation reactions at the Accelerator Laboratory of the University of Jyväskylä, Finland. The fusion products were selected using the gas-filled ion separator RITU and their decays were characterized using an array of detectors for charged particles and electromagnetic radiation known as GREAT. Prompt γ-ray transitions were detected and correlated with the decays using the JUROGAM II germanium detector array surrounding the target position. Results obtained from total Routhian surface (TRS) calculations suggest that α-decay fine structure and the associated hindrance factors may be a sensitive probe of even relatively small shape changes between the final states in the daughter nucleus.5 MoreReceived 13 October 2022Accepted 11 January 2023DOI:https://doi.org/10.1103/PhysRevC.107.014308Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI. Funded by Bibsam.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasAlpha decayLow & intermediate energy heavy-ion reactionsNuclear structure & decaysProperties150 ≤ A ≤ 189Nuclear Physics

Odd-odd neutron-rich rhodium isotopes studied with the double Penning trap JYFLTRAP

Precision mass measurements of neutron-rich rhodium isotopes have been performed at the JYFLTRAP Penning trap mass spectrometer at the Ion Guide Isotope Separator On-Line (IGISOL) facility. We report results on ground- and isomeric-state masses in $^{110,112,114,116,118}\mathrm{Rh}$ and the very first mass measurement of $^{120}\mathrm{Rh}$. The isomeric states were separated and measured for the first time using the phase-imaging ion-cyclotron-resonance (PI-ICR) technique. For $^{112}\mathrm{Rh}$, we also report new half-lives for both the ground state and the isomer. The results are compared to theoretical predictions using the BSkG1 mass model and discussed in terms of triaxial deformation.

Controlling the LCST-Phase Transition in Azobenzene-Functionalized Poly (N-Isopropylacrlyamide) Hydrogels by Light

Poly(N-isopropylacrylamide) PNIPAAm hydrogels were modified with a new azobenzene-containing co-monomer. In this work, light responsiveness as an additional functionality, is conceptualized to induce two phase transitions in the same material, which can be controlled by light. For a hydrogel with merely 2.5 mol% of this co-monomer, the lower critical solution transition temperature (LCST) was lowered by 12 °C (to 20 °C) compared to PNIPAAm (LCST at 32 °C), as analyzed by differential scanning calorimetry (DSC). The untreated unimodal endotherm split into a bimodal peak upon irradiation with UV-light, giving a second onset due to the switched (Z) isomer-rich regions, LCST*H2.5%-(Z) = 26 °C. On irradiation with 450 nm, leading to the reverse (Z) to (E) isomerization, the endotherm was also reversible. Thus, a photo-switchable hydrogel whose LCST and structure are tunable with the hydrophobicity-hydrophilicity of the (E) and (Z) isomeric state of azobenzene was obtained. The influence of the increase in the mol% of azoacrylate on the LCST was evaluated via DSC, in combination with NMR studies, UV-vis spectroscopy and control experiments with linear polymers. The large light-driven modulation of the LCST adds bistability in thermoresponsive hydrogels, which may open diverse applications in the field of soft robotics actuators.

Nuclear Isomers in the Heaviest Nuclei — the Odd Nucleon as a Sensitive Probe of Low-lying Nuclear Structure

Nuclear Isomers in the Heaviest Nuclei — the Odd Nucleon as a Sensitive Probe of Low-lying Nuclear Structure

Chemistry of nuclear spin isomers of the molecules: from the past of the Universe to emerging technologies

Chemistry of nuclear spin isomers of the molecules: from the past of the Universe to emerging technologies

Conformational characteristics of poly(3-hydroxyvalerate) (P3HV) and structure-property relationships of P3HV and poly(3-hydroxybutyrate).

Conformational analysis of biosynthetic and biodegradable poly(3-hydroxyvalerate) (P3HV), an analog of poly(3-hydroxybutyrate) (P3HB), was performed. The only structural difference between the two polymers consists in the side chain, which is either methyl (P3HB) or ethyl (P3HV). Molecular orbital calculations and NMR experiments were conducted on a monomeric model compound to determine the bond conformations of the main and side chains of P3HV. The refined rotational isomeric state (RIS) scheme was applied to derive configurational properties of P3HV. The characteristic ratio of P3HV (2.1-3.0) is smaller than that of P3HB (5.4-5.6), indicating greater conformational flexibility of the P3HV chain. The increased flexibility due to the internal rotation of the ethyl side group of P3HV results in a lower equilibrium melting point (130 °C) compared with P3HB (203 °C). The RIS calculations on P3HV also suggested its potential for rubber-like properties. Periodic density functional theory calculations were used to optimize the crystal structures of P3HB and P3HV and obtain their elastic moduli. Three-dimensional Young's modulus distributions of both crystals are closer to isotropic than anisotropic. In conclusion, the material design and usage of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) are discussed.

A photoresponsive gold catalyst based on azobenzene-functionalized NHC ligands.

An azobenzene-bearing N-heterocyclic carbene-based gold catalyst is reported of which the reactivity in a cyclization reaction depends on the isomeric state of the azobenzene. The configurations of the catalyst can be reversibly switched by light and are stable during the reaction, effectively leading to a switchable catalyst system.

Excitation of Isomeric States in \((n,2n)\) and \((\gamma ,n)\) Reactions on \(^{198,200}\)Hg Nuclei

Excitation of Isomeric States in \((n,2n)\) and \((\gamma ,n)\) Reactions on \(^{198,200}\)Hg Nuclei

Isomeric Lifetime Measurement in the Neutron-rich 189Ta

Isomeric states of the neutron-rich isotope 18973Ta116 were populated via fragmentation of a primary beam of 208Pb ions at 1 GeV/u impinging on a 9Be target at GSI, Darmstadt, Germany. The isotopes of interest were separated, identified and delivered to the DESPEC setup. Two isomers were deduced in 189Ta116 and their lifetimes were measured based on the γ-ray time distributions.