Search Results (10)

High-spin nuclear isomers in $N\approx Z$ nuclei between doubly magic ${}^{40}$Ca and ${}^{56}$Ni provide an excellent testing ground for the nuclear shell model and questions related to isospin symmetry breaking in the vicinity of the proton drip line. The purpose of the present study is to investigate the possibility of weak electromagnetic decay branches along the decay paths of the 6526-keV ${10}^{+}$ isomer in ${}^{54}$Fe. The isomer was strongly populated by means of the fusion-evaporation reaction ${}^{24}$Mg(${}^{36}$Ar,$\alpha 2p$)${}^{54m}$Fe. The Gammasphere array was used to detect $\gamma$-ray cascades emitted from the isomeric state. By means of $\gamma \gamma \gamma$ coincidences, weak non-yrast decay branches can be discriminated, with the isomer’s half-life confirmed at $T_{1/2}=363\left(4\right)$ ns. The yrast $6_1^{+}\to 2_1^{+}$ $E4$ cross-over transition was interrogated. The observations are compared with shell-model calculations. Full article

A π-conjugated polymer (PBQT) containing bis-(2-ethylhexyloxy)-benzo [1,2-b’] bithiophene (BDT) units alternated with a quinoline-vinylene trimer was obtained by the Stille reaction. The chemical structure of the polymer was verified by nuclear magnetic resonance (¹H NMR), Fourier transform infrared (FT-IR), and mass spectroscopy (MALDI-TOF). The intrinsic photophysical properties of the solution were evaluated by absorption and (static and dynamic) fluorescence. The polymer PBQT exhibits photochromism with a change in absorption from blue (449 nm) to burgundy (545 nm) and a change in fluorescence emission from green (513 nm) to orange (605 nm) due to conformational photoisomerization from the trans to the cis isomer, which was supported by theoretical calculations DFT and TD-DFT. This optical response can be used in optical sensors, security elements, or optical switches. Furthermore, the polymer forms spin-coated films with absorption properties that cover the entire visible range, with a maximum near the solar emission maximum. The frontier molecular orbitals, HOMO and LUMO, were calculated by cyclic voltammetry, and values of −5.29 eV and −3.69, respectively, and a bandgap of 1.6 eV were obtained, making this material a semiconductor with a good energetic match. These properties could suggest its use in photovoltaic applications. Full article

The application of parahydrogen gas to enhance the magnetic resonance signals of a diversity of chemical species has increased substantially in the last decade. Parahydrogen is prepared by lowering the temperature of hydrogen gas in the presence of a catalyst; this enriches the para spin isomer beyond its normal abundance of 25% at thermal equilibrium. Indeed, parahydrogen fractions that approach unity can be attained at sufficiently low temperatures. Once enriched, the gas will revert to its normal isomeric ratio over the course of hours or days, depending on the surface chemistry of the storage container. Although parahydrogen enjoys long lifetimes when stored in aluminum cylinders, the reconversion rate is significantly faster in glass containers due to the prevalence of paramagnetic impurities that are present within the glass. This accelerated reconversion is especially relevant for nuclear magnetic resonance (NMR) applications due to the use of glass sample tubes. The work presented here investigates how the parahydrogen reconversion rate is affected by surfactant coatings on the inside surface of valved borosilicate glass NMR sample tubes. Raman spectroscopy was used to monitor changes to the ratio of the (J: 0 → 2) vs. (J: 1 → 3) transitions that are indicative of the para and ortho spin isomers, respectively. Nine different silane and siloxane-based surfactants of varying size and branching structures were examined, and most increased the parahydrogen reconversion time by 1.5×–2× compared with equivalent sample tubes that were not treated with surfactant. This includes expanding the pH₂ reconversion time from 280 min in a control sample to 625 min when the same tube is coated with (3-Glycidoxypropyl)trimethoxysilane. Full article

Nuclear isomers are the metastable excited states of nuclei. The isomers can be categorized into a few classes including spin, seniority, K, shape and fission isomers depending upon the hindrance mechanisms. In this paper, we aim to present an overview of seniority isomers, which is a category related to the seniority quantum number. The discussion is mainly based on the concepts of seniority and generalized seniority. Various aspects of seniority isomers and their whereabouts have been covered along with the situations where seniority mixing prevents the isomerism. Full article

It is well known that the association of parahydrogen (pH₂) with an unsaturated molecule or a transient metalorganic complex can enhance the intensity of NMR signals; the effect is known as parahydrogen-induced polarization (PHIP). During recent decades, numerous methods were proposed for converting pH₂-derived nuclear spin order to the observable magnetization of protons or other nuclei of interest, usually ¹³C or ¹⁵N. Here, we analyze the constraints imposed by the topological symmetry of the spin systems on the amplitude of transferred polarization. We find that in asymmetric systems, heteronuclei can be polarized to 100%. However, the amplitude drops to 75% in A₂BX systems and further to 50% in A₃B₂X systems. The latter case is of primary importance for biological applications of PHIP using sidearm hydrogenation (PHIP-SAH). If the polarization is transferred to the same type of nuclei, i.e., ¹H, symmetry constraints impose significant boundaries on the spin-order distribution. For AB, A₂B, A₃B, A₂B₂, AA’(AA’) systems, the maximum average polarization for each spin is 100%, 50%, 33.3%, 25%, and 0, respectively, (where A and B (or A’) came from pH₂). Remarkably, if the polarization of all spins in a molecule is summed up, the total polarization grows asymptotically with ~1.27$\sqrt{N}$ and can exceed 2 in the absence of symmetry constraints (where $N$ is the number of spins). We also discuss the effect of dipole–dipole-induced pH₂ spin-order distribution in heterogeneous catalysis or nematic liquid crystals. Practical examples from the literature illustrate our theoretical analysis. Full article

Symmetry forms the foundation of combinatorial theories and algorithms of enumeration such as Möbius inversion, Euler totient functions, and the celebrated Pólya’s theory of enumeration under the symmetric group action. As machine learning and artificial intelligence techniques play increasingly important roles in the machine perception of music to image processing that are central to many disciplines, combinatorics, graph theory, and symmetry act as powerful bridges to the developments of algorithms for such varied applications. In this review, we bring together the confluence of music theory and spectroscopy as two primary disciplines to outline several interconnections of combinatorial and symmetry techniques in the development of algorithms for machine generation of musical patterns of the east and west and a variety of spectroscopic signatures of molecules. Combinatorial techniques in conjunction with group theory can be harnessed to generate the musical scales, intensity patterns in ESR spectra, multiple quantum NMR spectra, nuclear spin statistics of both fermions and bosons, colorings of hyperplanes of hypercubes, enumeration of chiral isomers, and vibrational modes of complex systems including supergiant fullerenes, as exemplified by our work on the golden fullerene C_150,000. Combinatorial techniques are shown to yield algorithms for the enumeration and construction of musical chords and scales called ragas in music theory, as we exemplify by the machine construction of ragas and machine perception of musical patterns. We also outline the applications of Hadamard matrices and magic squares in the development of algorithms for the generation of balanced-pitch chords. Machine perception of musical, spectroscopic, and symmetry patterns are considered. Full article

Hydrogen molecules exist in the form of two distinct isomers that can be interconverted by physical catalysis. These ortho and para forms have different thermodynamical properties. Over the last century, the catalysts developed to convert hydrogen from one form to another, in laboratories and industries, were magnetic and the interpretations relied on magnetic dipolar interactions. The variety concentration of a sample and the conversion rates induced by a catalytic action were mostly measured by thermal methods related to the diffusion of the o-p reaction heat. At the turning of the new century, the nature of the studied catalysts and the type of measures and motivations completely changed. Catalysts investigated now are non-magnetic and new spectroscopic measurements have been developed. After a fast survey of the past studies, the review details the spectroscopic methods, emphasizing their originalities, performances and refinements: how Infra-Red measurements characterize the catalytic sites and follow the conversion in real-time, Ultra-Violet irradiations explore the electronic nature of the reaction and hyper-frequencies driving the nuclear spins. The new catalysts, metallic or insulating, are detailed to display the operating electronic structure. New electromagnetic mechanisms, involving energy and momenta transfers, are discovered providing a classification frame for the newly observed reactions. Full article

The selective production of p-xylene and other aromatics starting from sugars and bioderived ethylene offers great promise and can eliminate the need for separation of xylene isomers, as well as decreasing dependency on fossil resources and CO₂ emissions. Although the reaction is known, the microporosity of traditional commercial zeolites appears to be a limiting factor. In this work, we demonstrate for the first time that simply desilication of microporous commercial zeolites by a simple NaOH treatment can greatly enhance conversion and selectivity. The [4 + 2] Diels–Alder cycloaddition of 2,5-dimethylfuran with ethylene in a pressurised reactor was investigated using a series of H-ZSM-5 catalysts with SiO₂/Al₂O₃ ratios 30 and 80 with increasing pore size induced by desilication. X-ray diffraction, scanning electron microscopy, ²⁷Al magic-angle spinning nuclear magnetic resonance, temperature programmed desorption of ammonia, and nitrogen physisorption measurements were used to characterise the catalysts. The enhancement of conversion was observed for all desilicated samples compared to the untreated zeolite, and increases in temperature and ethylene pressure significantly improved both dimethylfuran conversion and selectivity to p-xylene due to the easier desorption from the zeolite’s surface and the augmented cycloaddition rate, respectively. A compromise between acidity and mesoporosity was found to be the key to enhancing the activity and maximising the selectivity in the production of p-xylene from 2,5-dimethylfuran. Full article

The nuclear inelastic scattering signatures of the low-spin centers of the methanosulphonate, tosylate, and perchlorate salts of the spin crossover polymer ([Fe(II)(4-amino-1,2,4-triazole)₃]²⁺)_n have been compared for the low-spin phase, for the mixed high-spin and low-spin phases, as well as for Zn(II) diluted samples. Within this series a change in the vibrational pattern in the 320–500 cm⁻¹ region is observed. Significant shifts and decreasing intensity of bands at ~320 cm⁻¹ and bands over 400 cm⁻¹ are observed as the molar fraction of the low-spin (LS) centers decrease. Density functional theory calculations using Gaussian09 (B3LYP/CEP-31G) for pentameric, heptameric, and nonameric model molecules yielded the normal modes of several spin isomers: these include the all high-spin (HS) and the all low-spin (LS) configuration but also mixtures of LS and HS centers, with a special focus on those with LS centers in a HS matrix and vice versa. The calculations reproduce the observed spectral changes and show that they are caused by strain extorted on a LS Fe(II) center by its HS neighbors due to the rigid character of the bridging aminotriazole ligand. Additionally, the normal mode analysis of several spin isomers points towards a coupling of the vibrations of the iron centers of the same spin: the metal-ligand stretching modes of the all LS and the all HS spin isomers reveal a collective character: all centers of the same spin are involved in characteristic normal modes. For the isomers containing both LS and HS centers, the vibrational behavior corresponds to two different subsets (sublattices) the vibrational modes of which are not coupled. Finally, the calculation of nuclear inelastic scattering data of spin isomers containing a ca. 1:1 mixture of HS and LS Fe(II) points towards the formation of blocks of the same spin during the spin transition, rather than to alternate structures with a HS-LS-HS-LS-HS motif. Full article

A homodimeric, growth-related and time-keeping hydroquinone oxidase (ENOX1) of the eukaryotic cell surface capable of oxidizing intracellular NADH exhibits properties of the ultradian driver of the biological 24 h circadian clock by exhibiting a complex 2 + 3 set of oscillations of copper salts and appear to derive from periodic variations in the ratio of ortho and para nuclear spins of the paired hydrogen atoms of the elongated octahedral structure of the ENOX1 protein bound copper II hexahydrates. A corollary of these observations is that the ortho/para oscillations must occur in a highly synchronized matter. Our findings suggest that water molecules communicate with each other via very low frequency electromagnetic fields and that these fields also appear to be generated by the energetics of the synchronous ortho to para interconversions of the nuclear spin pairs of the water hydrogens. Further evidence for energy absorbed and emitted by water and correlated with ortho/para oscillations of ortho/para spin pairs of water hydrogens is indicated from the auto-oscillations in water luminescence. The emissions oscillate with period lengths of 18.8 min that agree with our previously found period of oscillation of about 18 min for pure water, reflective of ortho to para spin isomers based on measurements of redox potential. The period length of pure water (increased by about 25% in D₂O) and varies depending on the dominant cation present (copper salts in solution are unique in that the period length is exactly 24 min). Synchrony is maintained through generation of and response to LFEMF generated by the ortho-para spin pairs. Changes in redox potential sufficient to catalyze NADH oxidation were used to monitor synchronous water oscillations that appear to extend indefinitely over great distances in contiguous bodies of either still or flowing water. Adjacent out-of-phase water samples contained in thin plastic cuvettes auto-synchronize in a matter of seconds when placed side by side. Potential applications from water treatment along with opportunity related to human health are anticipated to derive from a better understanding of how water synchrony is generated and maintained, and to be aided by methodological advances in measurement and analysis. Full article