A Tale of Two Tails: Rotational Spectroscopy of N-Ethyl Maleimide and N-Ethyl Succinimide.

Broadband microwave spectra of N-ethyl maleimide (NEM) and N-ethyl succinimide (NES) have been recorded using chirped pulse Fourier transform microwave spectroscopy in the Ka-band (26.5-40 GHz). The spectra for both molecules were fit to a Watson A-reduced Hamiltonian in the Ir representation to obtain best fit experimental rotational constants (NEM: A0 = 2143.1988(29), B0 = 1868.7333(22), C0 = 1082.98458(36); NES: A0 = 2061.47756(14), B0 = 1791.73517(12), C0 = 1050.31263(11)), centrifugal distortion constants, and nuclear quadrupole coupling constants. While the heavy atoms of the five-membered ring of both molecules are planar, the ethyl chain has its terminal methyl group perpendicular to the ring. Along the relaxed potential energy curve for the ethyl dihedral angle (θ1 = C(6)-C(5)-N-C(4)), the ethyl group experiences significant steric strain when it is in the plane of the ring, associated with the interaction of the ethyl group with the two carbonyl oxygens. This leads to calculated barriers of θ1 = 1469 cm-1 and θ1 = 1680 cm-1 in N-ethyl maleimide and N-ethyl succinimide, respectively.

Quantitative Study of Enantiomer-Specific State Transfer.

We here report on a quantitative study of enantiomer-specific state transfer, performed in a pulsed, supersonic molecular beam. The chiral molecule 1-indanol is cooled to low rotational temperatures (1-2 K) and a selected rotational level in the electronic and vibrational ground state of the most abundant conformer is depleted via optical pumping on the S_{1}←S_{0} transition. Further downstream, three consecutive microwave pulses with mutually perpendicular polarizations and with a well-defined duration and phase are applied. The population in the originally depleted rotational level is subsequently monitored via laser-induced fluorescence detection. This scheme enables a quantitative comparison of experiment and theory for the transfer efficiency in what is the simplest enantiomer-specific state transfer triangle for any chiral molecule, that is, the one involving the absolute ground state level, |J_{K_{a}K_{c}}⟩=|0_{00}⟩. Moreover, this scheme improves the enantiomer enrichment by over an order of magnitude compared to previous works. Starting with a racemic mixture, a straightforward extension of this scheme allows one to create a molecular beam with an enantiomer-pure rotational level, holding great prospects for future spectroscopic and scattering studies.

Bond Length Alternation and Internal Dynamics in Model Aromatic Substituents of Lignin.

Broadband microwave spectra were recorded over the 2-18 GHz frequency range for a series of four model aromatic components of lignin; namely, guaiacol (ortho-methoxy phenol, G), syringol (2,6-dimethoxy phenol, S), 4-methyl guaiacol (MG), and 4-vinyl guaiacol (VG), under jet-cooled conditions in the gas phase. Using a combination of 13 C isotopic data and electronic structure calculations, distortions of the phenyl ring by the substituents on the ring are identified. In all four molecules, the rC(1)-C(6) bond between the two substituted C-atoms lengthens, leading to clear bond alternation that reflects an increase in the phenyl ring resonance structure with double bonds at rC(1)-C(2) , rC(3)-C(4) and rC(5)-C(6) . Syringol, with its symmetric methoxy substituents, possesses a microwave spectrum with tunneling doublets in the a-type transitions associated with H-atom tunneling. These splittings were fit to determine a barrier to hindered rotation of the OH group of 1975 cm-1 , a value nearly 50 % greater than that in phenol, due to the presence of the intramolecular OH⋅⋅⋅OCH3 H-bonds at the two equivalent planar geometries. In 4-methyl guaiacol, methyl rotor splittings are observed and used to confirm and refine an earlier measurement of the three-fold barrier V3 =67 cm-1 . Finally, 4-vinyl guaiacol shows transitions due to two conformers differing in the relative orientations of the vinyl and OH groups.

High-resolution UV spectroscopy of 1-indanol.

We report on rotationally resolved laser induced fluorescence (LIF) and vibrationally resolved resonance-enhanced multiphoton ionization (REMPI) spectroscopy of the chiral molecule 1-indanol. Spectra of the S1← S0 electronic transition are recorded in a jet-cooled, pulsed molecular beam. Using two time-delayed pulsed lasers, the lifetimes of the S1 state of the two most stable conformers, referred to as eq1 and ax2, have been determined. The S1← S0 origin bands of these conformers as well as the transition to a vibrationally excited level in the S1 state of eq1 are recorded with full rotational resolution (25 MHz observed linewidth) by measuring the LIF intensity following excitation with a tuneable, narrowband cw laser. On selected rotationally resolved electronic transitions, Lamb-dips are measured to confirm the Lorentzian lifetime-contribution to the observed lineshapes. The rotationally resolved S1← S0 origin band of a neon-complex of eq1 is measured via LIF as well. The fit of the rotationally resolved LIF spectra of the origin bands to those of an asymmetric rotor yields a standard deviation of about 6 MHz. The resulting spectroscopic parameters are tabulated and compared to the outcome of ab initio calculations. For both conformers as well as for the Ne-eq1 complex, the geometric structures in the S0 and S1 states are discussed. For all systems, the transition dipole moment is mainly along the a-axis, the contributions along the b- and c-axes being about one order of magnitude smaller.

Propagating molecular rotational coherences through single-frequency pulses in the strong field regime.

In the weak-field limit in which microwave spectroscopy is typically carried out, an application of a single-frequency pulse that is resonant with a molecular transition will create a coherence between the pair of states involved in the rotational transition, producing a free-induction decay (FID) that, after Fourier transform, produces a molecular signal at that same resonance frequency. With the advent of chirped-pulse Fourier transform microwave methods, the high-powered amplifiers needed to produce broadband microwave spectra also open up other experiments that probe the molecular response in the high-field regime. This paper describes a series of experiments involving resonant frequency pulses interrogating jet-cooled molecules under conditions of sufficient power to Rabi oscillate the two-state system through many Rabi cycles. The Fourier-transformed FID shows coherent signal not only at the applied resonant frequency but also at a series of transitions initially connected to the original one by sharing an upper or lower level with it. As the duration of the single-frequency excitation is increased from 250 to 1500 ns, the number of observed off-resonant, but dipole-allowed, molecular coherences grow. The phenomenon is quite general, having been demonstrated in Z-phenylvinylnitrile, E-phenylvinylnitrile (E-PVN), benzonitrile, guaiacol, and 4-pentynenitrile. In E-PVN, the highest power/longest pulse duration, coherent signal is also present at energetically nearby but not directly connected transitions. Even in molecular samples containing more than one independent species, only transitions due to the single species responsible for the original resonant transition are present. We develop a time-dependent model of the molecular/photon system and use it in conjunction with the experiment to test possible sources of the phenomenon.

Structural Characterization of Phenoxy Radical with Mass-Correlated Broadband Microwave Spectroscopy.

A combination of broadband microwave spectroscopy and VUV photoionization time-of-flight mass spectra has been used to record rotational spectra of the prototypical phenoxy radical, its per-deuterated isotopomers, and the full set of singly 13C-substituted analogues. Rotational parameters associated with the fits to the full set of isotopomers produce a highly accurate r0 structure for the phenoxy radical. High-level ab initio calculations accurately reproduce the rotational constants and spin-rotation parameters. The structure of the phenoxy radical is distinctly quinoidal, with delocalization of the unpaired electron spin density on the oxygen and phenyl ring. The fitted Fermi contact terms for the 13C atoms reflect a weighting of resonance structures that is 27% on the O atom, 21.5% on each of the two ortho C's, and 30% on the para C, providing a quantitative measure of its sites for subsequent reactions that will control its abundances in combustion and atmospheric environments.

Broadband Microwave Spectroscopy of 2-Furanyloxy Radical: Primary Pyrolysis Product of the Second-Generation Biofuel 2-Methoxyfuran.

Broadband microwave spectra over the 2-18 GHz range have been recorded for the resonance-stabilized 2-furanyloxy radical, formed in the first step of pyrolysis of the second-generation biofuel 2-methoxyfuran by methyl loss. Using a flash pyrolysis source attached to a pulsed valve, a 0.7% mixture of 2-methoxyfuran in argon was pyrolyzed at a series of temperatures ranging from 300 to 1600 K. Subsequent cooling in a supersonic expansion produced rotational temperatures of ∼2 K in the interrogation region. Using chirped-pulse Fourier transform microwave (CP-FTMW) methods, combined with strong-field coherence breaking (SFCB), a set of transitions due to the radical were identified and assigned. The experimental rotational constants ( A = 8897.732(93), B = 4019.946(24), C = 2770.321(84)), centrifugal distortion constants, and spin-rotation coupling constants have been determined for the radical and compared with ab initio predictions at the CCSD(T) level of theory. Compared to the 2-methoxyfuran precursor, the 2-furanyloxy radical has allylic C-C bond lengths intermediate between single and double bonds, a shortened C(5)-O(6) bond characteristic of partial double-bond character, and an O(1)-C(5)-O(6) bond angle of 121°, which resembles the O-C-O angle of an ester. Atomic spin densities extracted from the calculations confirm that the 2-furanyloxy radical is best viewed as a carbon-centered allylic lactone radical, with 80% of the spin density on the two allylic carbons and 20% on the pendant O(6) atom.

Protocolo para el análisis funcional de prótesis para pacientes con amputación parcial de pie / Protocol for the Functional Analysis of Prosthesis in Patients with Partial Foot Amputation

En la actualidad el desarrollo de prótesis presenta problemas que aún no se han solucionado por completo. A pesar de que se han desarrollado varios estudios enfocados a evaluar el funcionamiento de las prótesis, los trabajos que se presentan en la literatura se realizan con suposiciones de carga, de materiales, e incluso se practican bajo condiciones estáticas. La técnica de correlación de imágenes digitales ha sido útil en diversas aplicaciones, pero ha sido poco explorada en el ambiente de las prótesis. En este trabajo se presenta una técnica capaz de medir la deformación real en sistemas protésicos de pacientes amputados, bajo condiciones de carga y postura reales. Empleando el método de correlación de imágenes digitales es posible evaluar la prótesis del paciente sin necesidad de instrumentarla o modificarla. Además es posible conocer los principales puntos de deformación sin tener que fracturar la pieza. Con esta técnica es posible medir las principales zonas de deformación de un sistema protésico, con la ventaja de que la evaluación se pueden llevar a cabo aplicando cargas y posturas reales de un paciente en un análisis dinámico.

At present, the development of prostheses presents problems that have yet to be completely solved. Despite that various studies have been developed to evaluate the functioning of these prostheses, the works presented in the literature are conducted with suppositions of burden, of materials, and are even practiced under static conditions. The technique of Digital image correlation (DIC) has been useful in diverse applications, but has been scarcely explored in the ambience of prostheses. In this work, we present a technique capable of measuring the real deformation of prosthetic systems in patients with amputations, under real conditions of load and posture. Employing the DIC method, it is possible to evaluate a patient?s prosthesis without the need for instrumenting or modifying it. In addition, it is possible to know the main points of deformation without having to ultimate load the piece. With this technique, it is possible to measure the prosthetic system?s main deformation zones, with the advantage that evaluation can be performed applying the real loads and postures of a patient in a dynamic analysis.

[Value of delayed skin test in elderly patients]. / Valor de la prueba cutánea tardía en pacientes de la tercera edad.

BACKGROUND: Retarded cutaneous hypersensitivity to several antigens has been studied in human of different ages and in people older than 60 years a diminishment in response to tests measuring retarded hypersensitivity has been observed. OBJECTIVE: To determine the pattern of response to tests of retarded hypersensitivity in an apparently healthy sample of Cuban population resident at La Habana City, by application of a group of cutaneous tests with national antigens. MATERIAL AND METHODS: Intradermal tests were applied to 87 subjects (69 women and 18 men) between 60 and 89 years old, without frequent infection antecedents. All subjects were submitted to clinical history and analysis in order to discard diseases that may alter the study proposal. Response grade was determined by summing media of induration diameters, which was denominated total media punctuation. RESULTS: In all age groups total media punctuation was lightly higher in women, in both control and study groups, excepting age group of 80-89 years. CONCLUSION: By virtue of there are few indicators of health for old people, the group of tests proposed in this article may be a good predictive indicator of morbidity and mortality in old patients.

Estrés y alteraciones de la reacción inmunitaria en sujetos de la tercera edad / Stress and alterations of the immune reaction in elderly subjects

La evaluación de algunos aspectos de la reacción inmunitaria en el anciano estresado fue la finalidad de este estudio que se realizó a 96 personas de la tercera edad. Los sujetos de estudio se dividieron por grupos de edades a partir de los 60 años, tomándose el grupo de edades a partir de los 60 años, tomándose el grupo de ancianos no estresados como grupo testigo. No hubo diferencias significativas en las concentraciones de inmunoglobulina A, G, M, en el seno de la población estudiada. Se encontraron elteraciones significativas en la prueba de formación de roseta espontánea del grupo estresado

[Stress and changes in immune response in elderly subjects]. / Estrés y alteraciones de la reacción inmunitaria en sujetos de la tercera edad.

The evaluation of different aspects of the immune response in stress in the aged was the objective of our study, that was done with 96 persons of the third age. They were divided in different age groups since 60 years old. No significative differences in the concentrations of immunoglobulin A,G and M were found. Important disorders were detected in a spontaneous rosette.