Ring Expansion Of Alkylidenecarbenes Derived From Lactams, Lactones, And Thiolactones Into Strained Heterocyclic Alkynes: A Theoretical Study

Strained cycloalkynes are of considerable interest to theoreticians and experimentalists, and possess much synthetic value as well. Herein, a series of cyclic alkylidenecarbenes—formally obtained by replacing the carbonyl oxygen of four-, five-, and six-membered lactams, lactones, and thiolactones with a divalent carbon—were modeled at the CCSD(T)/cc-pVTZ//B3LYP/6-311+G** and CCSD(T)/cc-pVTZ//CCSD/6-311+G** levels of theory. The singlet carbenes were found to be more stable than the triplets. The strained heterocyclic alkynes formed by ring expansion of these singlet carbenes were also modeled. Interestingly, the C≡C bonds in the five-membered heterocycles, obtained from the rearrangement of β-lactam- and β-lactone-derived alkylidenecarbenes, displayed lengths intermediate between formal double and triple bonds. Furthermore, 2-(1-azacyclobutylidene)carbene was found to be nearly isoenergetic with its ring-expanded isomer, and 1-oxacyclopent-2-yne was notably higher in energy than its precursor carbene. In all other cases, the cycloalkynes were lower in energy than the corresponding carbenes. The transition states for ring-expansion were always lower for the 1,2-carbon shifts than for 1,2-nitrogen or oxygen shifts, but higher than for the 1,2-sulfur shifts. These predictions should be verifiable using carbenes bearing appropriate isotopic labels. Computed vibrational spectra for the carbenes, and their ring-expanded isomers, are presented and could be of value to matrix isolation experiments

Relativistic dynamical polarizability of hydrogen-like atoms

Using the operator representation of the Dirac Coulomb Green function the analytical method in perturbation theory is employed in obtaining solutions of the Dirac equation for a hydrogen-like atom in a time-dependent electric field. The relativistic dynamical polarizability of hydrogen-like atoms is calculated and analysed.Comment: 15 pages, 3 figures (not included, but hard copies are available upon request

The study of the guiding process for 10 keV electrons by planar Plexiglass surfaces

Experimental study of electron beam reflection from a single planar surface of Plexiglas was made. The distinct guiding effect for the part of the beam was observed for 10 keV electrons within angles of incidence from 0 to +3 degrees. The experiments using Poly plates showed a number of features of the process such as the dependence of the reflection on the plate surface quality and material of the surfaces, the divisions of the beam into two parts with different behaviour depend on tilt angle and the beam current value, the effect of an elevation angle of the beam in compare with initial beam trace at negative and zero tilt angles of the plat

Investigation of contactless electron transmission through dielectric channels

The effect of the contactless transmission (guiding) of 10 keV electrons through cylindrical dielectric channels and planar channels formed by glass platesis studiedyesBelgorod State Universit

Studying the interaction of 10 keV electrons with a dielectric surface

The grazing incidence interaction of a 10 keV electron beam with a planar surface of plexiglass is studied experimentally. Moreover, the electron passage through flat channels formed by such surfaces is inves tigated. The experiments reveal the presence of a guiding effect of the electron passage as in the case of a glass surfac

Generation and control of non-local quantum equivalent extreme ultraviolet photons

We present a high precision, self-referencing, common path XUV interferometer setup to produce pairs of spatially separated and independently controllable XUV pulses that are locked in phase and time. The spatial separation is created by introducing two equal but opposite wavefront tilts or using superpositions of orbital angular momentum. In our approach, we can independently control the relative phase/delay of the two optical beams with a resolution of 52 zs (zs = zeptoseconds). In order to explore the level of entanglement between the non-local photons, we compare three different beam modes: Bessel-like, and Gaussian with or without added orbital angular momentum. By reconstructing interference patterns one or two photons at a time we conclude that the beams are not entangled, yet each photon in the attosecond pulse train contains information about the entire spectrum. Our technique generates non-local, quantum equivalent XUV photons with a temporal jitter of 3 zs, just below the Compton unit of time of 8 zs. We argue that this new level of temporal precision will open the door for new dynamical QED tests. We also discuss the potential impact on other areas, such as imaging, measurements of non-locality, and molecular quantum tomography.Comment: 11 pages 5 figures and supplemental materials with 12 pages and 7 figure

Operator method in solving non-linear equations of the Hartree-Fock type

The operator method is used to construct the solutions of the problem of the polaron in the strong coupling limit and of the helium atom on the basis of the Hartree-Fock equation. $E_0=-0.1085128052\alpha^2$ is obtained for the polaron ground-state energy. Energies for 2s- and 3s-states are also calculated. The other excited states are briefly discussed.Comment: 7 page

Security-reliability analysis in CR-NOMA IoT network under I/Q imbalance

This paper presents a controllable analysis framework for evaluating the reliability and security of underlay cognitive radio networks (CRs) relying on non-orthogonal multiple access (NOMA). In such systems, a secondary base station (BS) transmits confidential information to multiple secondary users uniformly distributed in the presence of a nearby located external eavesdropper. Moreover, transmit power constraints are introduced to limit the interference to the primary imposed by cognitive base stations. As an effective approach of multiple input single output (MISO) systems, the transmit antenna selection (TAS) is selected in the BS to improve the secrecy performance of the primary networks. Furthermore, we first consider the impact of quadrature-phase imbalance (IQI) to characterize the secure performance of the considered network in practice. Then, the degraded performance is evaluated in terms of outage probability (OP), intercept probability (IP), and effective secrecy throughput (EST) of two NOMA users. The optimal EST can be achieved through simulations while the results of OP and IP provide guidelines in the design of IQI-aware CR-NOMA systems. Finally, the trade-off between OP and IP with transmit signal-to-noise ratio (SNR) at the BS is investigated for reflecting the security characteristic. Finally, the trade-off between OP and IP with transmit signal-to-noise ratio (SNR) at the BS is studied for displaying the security characteristic. Numerical results show that increasing the number of transmit antennas at the BS and other main parameters improves performance. Moreover, when the system parameters are reasonably set, the secondary NOMA user in CR-NOMA can be reached secure requirements regardless of the controlled IQI.Web of Science1111905611904

Noninvasive Liquid Diet Delivery of Stable Isotopes into Mouse Models for Deep Metabolic Network Tracing

Delivering isotopic tracers for metabolic studies in rodents without overt stress is challenging. Current methods achieve low label enrichment in proteins and lipids. Here, we report noninvasive introduction of 13C6-glucose via a stress-free, ad libitum liquid diet. Using NMR and ion chromatography-mass spectrometry, we quantify extensive 13C enrichment in products of glycolysis, the Krebs cycle, the pentose phosphate pathway, nucleobases, UDP-sugars, glycogen, lipids, and proteins in mouse tissues during 12 to 48 h of 13C6-glucose feeding. Applying this approach to patient-derived lung tumor xenografts (PDTX), we show that the liver supplies glucose-derived Gln via the blood to the PDTX to fuel Glu and glutathione synthesis while gluconeogenesis occurs in the PDTX. Comparison of PDTX with ex vivo tumor cultures and arsenic-transformed lung cells versus xenografts reveals differential glucose metabolism that could reflect distinct tumor microenvironment. We further found differences in glucose metabolism between the primary PDTX and distant lymph node metastases

Analytical study of the sth-order perturbative corrections to the solution to a one-dimensional harmonic oscillator perturbed by a spatially power-law potential Vper(x) = λxα

In this work, we present a rigorous mathematical scheme for the derivation of the sth-order perturbative corrections to the solution to a one-dimensional harmonic oscillator perturbed by the potential V-per(x) = lambda x(alpha), where alpha is a positive integer, using the non-degenerate time-independent perturbation theory. To do so, we derive a generalized formula for the integral I = integral(+infinity)(-infinity)x(alpha)exp(-x(2))H-n(x)H-m(x)d(x), where H-n(x) denotes the Hermite polynomial of degree n, using the generating function of orthogonal polynomials. Finally, the analytical results with alpha = 3 and alpha = 4 are discussed in detail and compared with the numerical calculations obtained by the Lagrange-mesh method