Advantages of Ferroelectrics as a Component of Heterostructures for Electronic Purposes: A DFT Insight.

The main advantage of using ferroelectric materials as a component of complex heterostructures is the ability to tune various properties of the whole system by means of an external electric field. In particular, the electric field may change the polarization direction within the ferroelectric material and consequently affect the structural properties, which in turn affects the electronic and magnetic properties of the neighboring material. In addition, ferroelectrics allow the electrostriction phenomenon to proceed, which is promising and can be used to affect the magnetic states of the interface state in the heterostructure through a magnetic component.

Synthesis and biological evaluation of fluoroquinolones containing a pyridoxine derivatives moiety.

We report herein the design, synthesis and biological evaluation of series of 7-substituted fluoroquinolones with pyridoxine derivatives. In vitro screening of antibacterial activity and toxicity of 39 synthesized fluoroquinolones defined compounds 7 and 28 as lead compounds for further investigations. On various clinical isolates lead compounds 7 and 28 exhibited antibacterial activity comparable with reference fluoroqinolones.

F electron nuclear double resonance (ENDOR) spectroscopy for distance measurements using trityl spin labels in DNA duplexes.

The combination of fluorine labeling and pulsed electron-nuclear double resonance (ENDOR) is emerging as a powerful technique for obtaining structural information about proteins and nucleic acids. In this work, we explored the capability of Mims F ENDOR experiments on reporting intermolecular distances in trityl- and F-labeled DNA duplexes at three electron paramagnetic resonance (EPR) frequencies (34, 94, and 263 GHz). For spin labeling, we used the hydrophobic Finland trityl radical and hydrophilic OX063 trityl radical.

Long-Lived Charge-Separated State in Naphthalimide-Phenothiazine Compact Electron Donor-Acceptor Dyads: Effect of Molecular Conformation Restriction and Solvent Polarity.

To study the charge separation (CS) and long-lived CS state, we prepared a series of dyads based on naphthalimide (NI, electron acceptor) and phenothiazine (PTZ, electron donor), with an intervening phenyl linker attached on the N-position of both moieties. The purpose is to exploit the electron spin control effect to prolong the CS-state lifetime by formation of the CS state, instead of the ordinary CS state, the spin-correlated radical pair (SCRP), or the free ion pairs. The electronic coupling magnitude is tuned by conformational restriction exerted by the methyl groups on the phenyl linker.

Preparation of Xanthene-TEMPO Dyads: Synthesis and Study of the Radical Enhanced Intersystem Crossing.

We prepared a rhodamine-TEMPO chromophore-radical dyad (RB-TEMPO) to study the radical enhanced intersystem crossing (REISC). The visible light-harvesting chromophore rhodamine is connected with the TEMPO (a nitroxide radical) via a C-N bond. The UV-vis absorption spectrum indicates negligible electron interaction between the two units at the ground state.

Experimental confirmation of the formation of a spin polariton in dilute solutions of paramagnetic particles.

Spin exchange during random bimolecular collisions of paramagnetic particles in dilute solutions leads to a surprising effect. Collective modes of motion of the average values of the transverse magnetization components (spin coherences) of subensembles of radicals with different resonant frequencies are formed. The elementary excitations of these modes can be considered as quasiparticles.

Observation of Long-Lived Charge-Separated States in Anthraquinone-Phenothiazine Electron Donor-Acceptor Dyads: Transient Optical and Electron Paramagnetic Resonance Spectroscopic Studies.

We prepared a series of phenothiazine (PTZ)-anthraquinone (AQ) electron donor-acceptor dyads to study the relationship between molecular structures and the possibility of charge transfer (CT) and intersystem crossing (ISC). As compared to the previously reported dyad with a direct connection of two units via a C-N single bond, the PTZ and AQ units are connected via a -phenylene or -biphenylene linker. Conformation restriction is imposed by attaching -methyl groups on the phenylene linker.

Upconversion Luminescence Response of a Single YVO:Yb, Er Particle.

We present the results of the luminescence response studies of a single YVO:Yb, Er particle of 1-µm size. Yttrium vanadate nanoparticles are well-known for their low sensitivity to surface quenchers in water solutions which makes them of special interest for biological applications. First, YVO:Yb, Er nanoparticles (in the size range from 0.

Origin of intersystem crossing in highly distorted organic molecules: a case study with red light-absorbing ,,,-boron-chelated Bodipys.

To explore the relationship between the twisted π-conjugation framework of aromatic chromophores and the efficacy of intersystem crossing (ISC), we have studied a ,,,-boron-chelated Bodipy derivative possessing a severely distorted molecular structure. Surprisingly, this chromophore is highly fluorescent, showing inefficient ISC (singlet oxygen quantum yield, = 12%). These features differ from those of helical aromatic hydrocarbons, where the twisted framework promotes ISC.

Long-Lived Charge Separated States in Anthraquinone-Phenothiazine Dyads: Synthesis and Study of the Photophysical Property by Using Transient Optical and Magnetic Resonance Spectroscopies.

In order to obtain long-lived charge separated (CS) states in electron donor-acceptor dyads, herein we prepared a series of anthraquinone (AQ)-phenothiazine (PTZ) dyads, with adamantane as the linker. UV-vis absorption spectra show negligible electronic interaction between the AQ and PTZ units at ground state, yet charge transfer (CT) emission bands were observed. Nanosecond transient absorption shows that the AQ state is populated upon photoexcitation for AQ-PTZ in cyclohexane (CHX), but in acetonitrile (ACN) a CS state is formed.

Integrated Multiresonator Quantum Memory.

We develop an integrated efficient multiresonator quantum memory scheme based on a system of three interacting resonators coupled through a common resonator to an external waveguide via switchable coupler. It is shown that high-precision parameter matching based on step-by-step optimization makes it possible to efficiently store the signal field and enables on-demand retrieval of the signal at specified time moments. Possible experimental implementations and practical applications of the proposed quantum memory scheme are discussed.

Approximate analytical expressions for the Carr-Purcell-Meiboom-Gill sequences: Decay rates and modulation zeros of the echo train and the relation between the T and T relaxation times.

Methods of multi-pulse sequences are widely used in magnetic resonance to study the local properties of magnetic particles and to increase the lifetime of spin coherence. Imperfect refocusing pulses lead to non-exponential signal decay due to the contribution of the coherence pathways in which T and T relaxation segments are mixed. Here, we present analytical approximations for echoes generated in the Carr-Purcell-Meiboom-Gill (CPMG) sequence.

Electron and nuclear magnetic properties near ZEFOZ region.

In the vicinity of spin level anti-crossings, electron-nuclear spin systems reveal characteristic features that have been investigated by electron paramagnetic resonance (EPR) methods, including electron spin echo envelope modulation (ESEEM). The spectral properties depend considerably on the difference, ΔB, between the magnetic field and the critical field at which the zero first-order Zeeman shift (ZEFOZ) occurs. To analyze the characteristic features near the ZEFOZ point, analytical expressions for the behavior of EPR spectra and ESEEM traces as a function of ΔB are obtained.

Covalent Functionalization of Black Phosphorus Nanosheets with Dichlorocarbenes for Enhanced Electrocatalytic Hydrogen Evolution Reaction.

Two-dimensional black phosphorus (BP) has emerged as a perspective material for various micro- and opto-electronic, energy, catalytic, and biomedical applications. Chemical functionalization of black phosphorus nanosheets (BPNS) is an important pathway for the preparation of materials with improved ambient stability and enhanced physical properties. Currently, the covalent functionalization of BPNS with highly reactive intermediates, such as carbon-free radicals or nitrenes, has been widely implemented to modify the material's surface.

The Ability of Some Polysaccharides to Disaggregate Lysozyme Amyloid Fibrils and Renature the Protein.

The deposition of proteins in the form of insoluble amyloid fibril aggregates is linked to a range of diseases. The supramolecular architecture of such deposits is governed by the propagation of β-strands in the direction of protofilament growth. In the present study, we analyze the structural changes of hen egg-white lysozyme fibrils upon their interactions with a range of polysaccharides, using AFM and FTIR spectroscopy.

In-Situ Electrochemical Exfoliation and Methylation of Black Phosphorus into Functionalized Phosphorene Nanosheets.

Two-dimensional black phosphorus (BP) has attracted great attention as a perspective material for various applications. The chemical functionalization of BP is an important pathway for the preparation of materials with improved stability and enhanced intrinsic electronic properties. Currently, most of the methods for BP functionalization with organic substrates require either the use of low-stable precursors of highly reactive intermediates or the use of difficult-to-manufacture and flammable BP intercalates.

Photoisomerization of 1,2-Di(4-pyridyl)ethylene According to NMR and UV Spectroscopy Data and Density Functional Modeling.

Photoisomerization of 1,2-di(4-pyridyl)ethylene under UV irradiation was studied by NMR and UV spectroscopy in solutions of acetone, acetonitrile and chloroform. It has been established that in the studied solutions under irradiation, geometric photoisomerization occurs: the trans-isomer transforms into the cis-isomer and then cyclization occurs. DFT modeling of the listed processes, states and UV absorption spectra of the sample in an acetonitrile solution was performed.

Synthesis of D-π-A'-π-A Chromophores with Quinoxaline Core as Auxiliary Acceptor and Effect of Various Silicon-Substituted Donor Moieties on Thermal and Nonlinear Optical Properties at Molecular and Material Level.

Novel D-π-A'-π-A chromophores with quinoxaline cores as auxiliary acceptors and various donor moieties (aniline, carbazole, phenothiazine, tetrahydroquinoline) containing bulky -butyldimethylsilyloxy (TBDMSO) groups and tricyanofuranyl (TCF) acceptors with bulky cyclohexylphenyl substituents were synthesized via eight- to nine-step procedures, and their photo-physical and thermal properties were investigated. The values of the chromophores' first hyperpolarizabilities were calculated in the framework of DFT at the M06-2X/aug-cc-pVDZ computational level; the effect of the introduction of the TBDMSO group into the donor fragment is shown to be inessential, as this group is not coupled to the π-conjugated system of the chromophore. The chromophore with the tetrahydroquinoline donor has a first hyperpolarizability value of 937 × 10 esu, which is the highest for the studied chromophores.

Engineering the Exchange Spin Waves in Graded Thin Ferromagnetic Films.

The results of experimental and theoretical studies of standing spin waves in a series of epitaxial films of the ferromagnetic Pd1−xFex alloy (0.02 < x < 0.11) with different distributions of the magnetic properties across the thickness are presented.

A two-site triplet exciton hopping model: Application to P.

A model is presented describing the effect on spin-polarized transient EPR signals caused by incoherent state hopping between two sites. It is shown that the size of the spin state space can be reduced by half to the subspace described by the site-average Hamiltonian and that the dynamics of the system results in a redistribution of the population between its eigenstates. Analytical expressions for the rates of population redistribution and the line shape are derived for the general case in which the back-and-forth rates are unequal.

Observation of the triplet energy transfer in orthogonal photoexcited iodinated-BODIPY dimers.

Intramolecular charge and energy transfer processes initiated by light absorption can change the photosensitization properties of molecular conjugates. Transient optical and electron paramagnetic resonance (TREPR) spectroscopies are well suited for the study of these processes. In the TREPR spectra of the triplet state of an iodinated BODIPY dimer, we have observed the effect of the averaging of the zero-field (ZFS) parameter , which becomes more efficient with increasing temperature.

Static and Resonant Properties and Magnetic Phase Diagram of LiMnTeO.

Physical properties of the mixed-valent tellurate of lithium and manganese, LiMn2TeO6, were investigated in measurements of ac and dc magnetic susceptibility χ, magnetization M, specific heat Cp, electron spin resonance (ESR), and nuclear magnetic resonance (NMR) in the temperature range 2−300 K under magnetic field up to 9 T. The title compound orders magnetically in two steps at T1 = 20 K and T2 = 13 K. The intermediate phase at T2 < T < T1 is fully suppressed by magnetic field µ0H of about 4 T.

DFT Insight into Conductive and Magnetic Properties of Heterostructures with BaTiO Overlayer.

The ab initio calculations of a heterostructure based on the ferroelectric phase of barium titanate and dielectrics lanthanum manganese (LaMnO) or silicon (Si) are presented. We analyze structures of BaTiO/LaMnO and BaTiO/Si interfaces, investigate magnetic properties and the impact of ferroelectric polarization. The use of ferroelectrics in the heterostructure plays a crucial role; in particular, ferroelectric polarization leads to the appearance of the conducting state at the interface and in the layers close to it.

Experimental Observation of a Peculiar Effect in Saturated Electron Paramagnetic Resonance Spectra Undergoing Spin Exchange. Magnetic Polariton?

We report the experimental observation of a spectral manifestation of a magnetic polariton that was theoretically predicted last year. This unprecedented manifestation is demonstrated not only for N-enriched peroxylamine disulfonate, a radical that adheres strictly to the assumptions of the theory, but also for a radical, 4-oxo-2,2,6,6-tetramethylpiperidine-;1-15N-1-oxyl, that departs somewhat from the assumptions, as well as the Galvinoxyl radical that represents a severe departure. The magnetic polariton is likely to be of interest to physical chemists in other fields because of the intrinsic advantage of a finite basis set in developing theories.

Origin of Negative Photoconductivity at the Interface of BaSrTiO/LaMnO/BaSrTiO Heterostructures.

The study of BaSrTiO/LaMnO/BaSrTiO heterostructures on a MgO substrate with BaSrTiO ferroelectric films revealed the occurrence of a metallic character of the temperature behavior of the resistance at a temperature less than 175 K. This behavior is associated with an increased charge concentration at the interface due to a discontinuity in the ferroelectric polarization at the interface between the films. At these temperatures, the effect of negative photoconductivity is observed under uniform illumination with the light of a selected spectral composition event on the surface of the ferroelectric film.