Photoabsorption in formaldehyde: Intensities and assignments in the discrete and continuous spectral intervals

Theoretical investigations of total and partial‐channel photoabsorption cross sections in molecular formaldehyde are reported employing the Stieltjes–Tchebycheff (S–T) technique and separated‐channel static‐exchange (IVO) calculations. Vertical one‐electron dipole spectra for the 2b_2(n), 1b_1(π), 5a_1(σ), 1b_2, and 4a_1 canonical molecular orbitals are obtained using Hartree–Fock frozen‐core functions and large basis sets of compact and diffuse normalizable Gaussians to describe the photoexcited and ejected electrons. The calculated discrete excitation spectra provide reliable zeroth‐order approximations to both valence and Rydberg transitions, and, in particular, the 2b_2(n) →nsa_1, npa_1, npb_2, and nda_2 IVO spectra are in excellent accord with recent experimental assignments and available intensity measurements. Convergent (S–T) photoionization cross sections in the static‐exchange (IVO) approximation are obtained for the 15 individual partial channels associated with ionization of the five occupied molecular orbitals considered. Resonance features in many of the individual‐channel photoionization cross sections are attributed to contributions from valencelike a_1σ^∗ (CO), a_1σ^∗ (CH), and b_2σ^∗ (CH)/π_y^∗ (CO) molecular orbitals that appear in the photoionization continua, rather than in the corresponding one‐electron discrete spectral intervals. The vertical electronic cross sections for ^1A_1→^1B_1, ^1B_2, and ^1A_1 excitations are in generally good accord with previously reported CI (S–T) predictions of continuum orbital assignments and intensities, although some discrepancies due to basis‐set differences are present in the ^1B_1 and ^1B_2 components, and larger discrepancies apparently due to channel coupling are present in the ^1A_1→^1A_1 cross section. Partial‐channel vertical electronic cross sections for the production of the five lowest parent‐ion electronic states are found to be in general agreement with the results of very recent synchrotron‐radiation photoelectron branching‐ratio measurements in the 20 to 30 eV excitation energy interval. Most important in this connection is the tentative verification of the predicted orderings in intensities of the partial‐ channel cross sections, providing support for the presence of a strong ka_1σ^∗ (CO) resonance in the (5a_1^(−1))^2A_1 channel. Finally, the total vertical electronic cross sections for absorption and ionization are in general accord with photoabsorption measurements, photoionization–mass–spectrometric studies, and the previously reported CI (S–T) calculations. Although further refined calculations including vibrational degrees of freedom and autoionization line shapes are required for a more precise quantitative comparison between theory and experiment, the present study should provide a reliable zeroth‐order account of discrete and continuum electronic dipole excitations in molecular formaldehyde

Intramolecular Hydrogen Bonding in Guanidinium and Potassium Hydrogen Malonates - an Infrared and X-Ray Diffraction Study

A new modification of potassium hydrogen malonate was obtained by crystallization from dimethylsulphoxide (DMSO)\u27 solution. Its infrared spectrum differs in its essential features from the spectra of the known modification crystallizing from water!-" but resemble those of guanidinium hydrogen malonate. Both spectra are interpreted in terms of strong, intramolecular hydrogen bonding, This is supported by the fact that the main features (CO and OH stretching) remain essentially unchanged on dissolution in DMSO and by the X-ray diffraction on guanidinium hydrogen malonate. The structure of its crystals was solved by the direct method and refined by full matrix least squares to R value of 0.044 for 453 observed reflections. The structure consists of planar guanidinium ions and hydrogen maleate residues containing short intramolecular, but asymmetric bonds of 2.407(3)A

Resonant ion-pair formation in electron recombination with HF^+

The cross section for resonant ion-pair formation in the collision of low-energy electrons with HF^+ is calculated by the solution of the time-dependent Schrodinger equation with multiple coupled states using a wave packet method. A diabatization procedure is proposed to obtain the electronic couplings between quasidiabatic potentials of ^1Sigma^+ symmetry for HF. By including these couplings between the neutral states, the cross section for ion-pair formation increases with about two orders of magnitude compared with the cross section for direct dissociation. Qualitative agreement with the measured cross section is obtained. The oscillations in the calculated cross section are analyzed. The cross section for ion-pair formation in electron recombination with DF^+ is calculated to determine the effect of isotopic substitution.Comment: 12 pages, 12 figure

Photoexcitation and ionization in molecular fluorine: Stieltjes–Tchebycheff calculations in the static-exchange approximation

Theoretical investigation of outer (1pig, 1piu, 3sigmag) and inner (2sigmau, 2sigmag) valence-shell electronic photoexcitation and ionization cross sections in molecular fluorine are reported employing separated-channel static-exchange calculations and Stieltjes–Tchebycheff (S–T) moment-theory techniques. The discrete vertical electronic 1pig excitation series are found to be in good agreement with recent spectral assignments and previously reported theoretical studies, and those for 1piu, 3sigmag, 2sigmau and 2sigmag excitations are in general accord with position and intensity estimates based on quantum-defect analysis. Certain of the partial-channel photoionization cross sections in F2 are seen to exhibit resonancelike features similar to those reported recently in related S–T studies of photoionization in N2, CO, and O2. The resonances can be attributed to valencelike and pre-Rydberg diabatic states that cross the outer limbs of appropriate Rydberg series and corresponding ionic-state potential curves as functions of internuclear coordinate, giving rise to large continuum transition intensities at the ground-state equilibrium internuclear separation. In contrast to the situation in N2, CO, and O2, however, there is no evidence of a resonance like sigma-->sigma* feature in the 3sigmag-->ksigmau photoionization channel in F2. Rather, this resonance in F2 appears as a strong N-->Vg transition below the 3sigmag ionization threshold, and the corresponding partial-channel photoionization cross section is seen to be structureless. Although experimental studies of partial-channel photoionization cross sections are apparently unavailable for comparison, the calculations reported here should provide reliable approximations to the dipole excitation/ionization spectra in F2, and are helpful in understanding and clarifying the dependences of photoionization spectra in light diatomic molecules on shell occupancy and equilibrium internuclear separation when compared with the results of previous studies of photoionization in N2, CO, and O2

To determ arise the pressure in instable movement of liquid in pipe

За результатами теоретичних і експериментальних досліджень було встановлено, що тиск, який виникає при неусталеному русі рідини суттєво залежить від внутрішньої структури потоку. Від критеріїв цієї структури залежать втрати енергії на тертя, а також стійкість ламінарного режиму течії. Отримані результати досліджень дозволяють визначати ці величини і врахувати їх вплив на процес розвитку неусталеної течії рідини.At planning of the water systems it is necessary to foresee facilities of their protecting from the increase of pressure. His unexpected increase is determined a calculation and going out from the value of working pressure an air of defence which provides safe exploitation of pipes is assumed. The purpose of the offered work are experimental and theoretical researches of increase of pressure at an unwithstand motion of liquid in pipes. It is set that pressure which arises up at non-stationary motion of liquid substantially depends on the underlying structure of stream. Here take such criteria, as distributing of speeds in the living cut of stream, mode of flow et al. On them the losses of energy depend on a friction, and also firmness of the mode of laminar of flow. Dependence is got between speed of passing of transient and increase of pressure in pipes. The results of researches allow to determine the criteria of underlying structure of stream and take into account their influence on the process of development of an unwithstand flow of liquid.В результате теоретических и экспериментальных исследований было установлено, что возникающее повышение давление во время неустановившегося движения жидкости во многом зависит от внутренней структуры потока. От критериев этой структуры зависят потери энергии на трение, а также устойчивость ламинарного режима течения. Получение результаты исследования позволяют определять эти величины и учитывать их влияние на процесс развития неустановившегося движения

Application of microfluidic chips in anticancer drug screening

With the continuous development of drug screening technology, new screening methodologies and technologies are constantly emerging, driving drug screening into rapid, efficient and high-throughput development. Microfluidics is a rising star in the development of innovative approaches in drug discovery. In this article, we summarize the recent years' progress of microfluidic chip technology in drug screening, including the developmental history, structural design, and applications in different aspects of microfluidic chips on drug screening. Herein, the existing microfluidic chip screening platforms are summarized from four aspects: chip structure design, sample injection and drive system, cell culture technology on a chip, and efficient remote detection technology. Furthermore, this review discusses the application and developmental prospects of using microfluidic chips in drug screening, particularly in screening natural product anticancer drugs based on chemical properties, pharmacological effects, and drug cytotoxicity.Peer reviewe

IR AND X-RAY PHOTOELECTRON SPECTROSCOPY OF V 2 O 5 , TiO 2 AND V/Ti-OXIDE SOL-GEL DERIVED FILMS INFRARDE^A IN RENTGENSKA FOTOELEKTRONSKA SPEKTROSKOPIJA V 2 O 5 , TiO 2 IN V/Ti-OKSIDNIH SOL-GEL FILMOV

Prejem rokopisa -received: 1998-12-06; sprejem za objavo -accepted for publication: 1998-12-14 V/Ti-oxide films were prepared by dip-coating from sols made by mixing of V-oxoisopropoxide and Ti-propoxide in V:Ti molar ratio in precursors 3:1, 1:1 and 1:3. Amorphous films were obtained after annealing at 300°C (1 h). IR spectroscopic analysis revealed that V=O stretching modes appeared at 1020 cm -1 in the IR spectrum of powder (V:Ti=1:1). However, in the IR spectra of a film with the same molar ratio the bands at 1008 and 914 cm -1 appeared suggesting the presence of V 4+ -O bonds. The new band at 790 cm -1 signalled the V-O-Ti bridging bonds connecting V-O and Ti-O polyhedra. XPS measurements confirmed that initial-state films contained V 5+ , V 4+ and Ti 4+ species, but at the film surface only V 5+ species existed. Sequential depth analysis of films performed with Ar + sputtering showed that the vanadium is reduced to 3+ oxidation state with progressive exposure while titanium is not affected. Key words: electrochromic (EC) devices, oxide films, IR spectroscopy, XPS, oxidation states, sputtering, sol-gel V/Ti-oksidne filme smo pripravili iz koloidnih raztopin V-oksoizopropoksida in Ti-propoksida v 2-propanolu s tehniko potapljanja. Molska razmerja V:Ti v prekurzorjih so zna{ala 3:1, 1:1 in 1:3. Amorfni filmi so nastali po segrevanju na 300°C (1h). V IR spektru pra{kastega vzorca (V:Ti = 1:1) so se valen~na nihanja V=O pojavila pri 1020 cm -1 . V IR spektru filma z istim molskim razmerjem pa se pojavita trakova pri 1008 c

Збільшення тертя у потоці Тейлора-Куетта під час використання натрій карбоксиметилцелюлози

The results of experimental investigations of the influence of the rotor eccentricity on the stator and the influence of the carboxymethyl cellulose solutions on the friction coefficient in the hydraulic brake with the control braking torque are presented. Hydraulic brakes are used in bench studies, because they are simple in design, have high energy intensity and can regulate the load and rotation of the shaft. When using hydraulic brakes, the power developed by the engine under study is spent on overcoming the forces of the hydrodynamic resistance of the friction of the rotor in the working fluid, heating it and converted into heat energy. In the experimental stand, the annular gap between the rotor with a diameter of 113 mm and a stator with a diameter of 142 mm was filled with water and aqueous solutions of carboxymethyl cellulose with the addition of sodium bicarbonate for stabilization. Mass concentrations of carboxymethyl cellulose were taken equal to 0.5; 1.0; 2.0; 4.0 %, sodium bicarbonate – 0.2 % by weight of solution. The annular gap between the surfaces of the cylinders, which corresponded to their coaxial location, was transformed into a closed confuser-diffuser with a change in the position of the outer cylinder. It was also found that with increasing of angular velocity, the difference between the dimensionless torque for water and the aqueous solutions of carboxymethyl cellulose increases with a relative width of the gap equal to 1.0. The dependence of the coefficient of friction on the Reynolds number, on the width of the gap between the rotor and stator and on the concentration of aqueous solutions of carboxymethyl cellulose was found. As the Reynolds number increases, a decrease in the coefficient of friction for the investigated concentrations of solutions of carboxymethyl cellulose is observed. At constant values of the Reynolds number with an increase in the concentration of studied solutions of carboxymethyl cellulose, an increase in the coefficient of friction compared with water was obtained. With a decrease in the gap width, an increase in the friction coefficient was obtained for all the studied concentrations of carboxymethyl cellulose solutions. The obtained results indicate the possibility of adjusting the brake torque of the hydraulic brake by changing the eccentricity between the rotor and the stator and can be used in the design of the hydraulic brakes with the adjustable brake torque.Представлено результати експериментальних досліджень впливу ексцентриситету ротора відносно статора та розчинів карбоксиметилцелюлози на коефіцієнт тертя в гідрогальмі з регулювальним гальмівним моментом. Кільцевий проміжок між ротором із діаметром 113 мм і статором із діаметром 142 мм заповнювали водними розчинами карбоксиметилцелюлози з додаванням гідрокарбонату натрію для стабілізації. Масові концентрації карбоксиметилцелюлози – 0,5; 1,0; 2,0; 4,0 %, гідрокарбонату натрію – 0,2 % від маси розчину. Кільцевий проміжок між поверхнями циліндрів, який відповідав коаксіальному їх розташуванню, трансформувався у замкнений конфузорно-дифузорний внаслідок зміни положення зовнішнього циліндра відносно внутрішнього. Виявлено залежність коефіцієнта тертя від числа Рейнольдса, ширини проміжку між ротором і статором під час їх аксіального розташування та концентрації водних розчинів карбоксиметилцелюлози. Зі збільшенням числа Рейнольдса спостережено зменшення коефіцієнта тертя для досліджених концентрацій розчинів карбоксиметилцелюлози. За сталих значень числа Рейнольдса зі збільшенням концентрації розчинів карбоксиметилцелюлози отримано збільшення коефіцієнта тертя, порівняно з водою. У разі зменшення ширини проміжку одержано збільшення коефіцієнта тертя для всіх досліджених концентрацій розчинів карбоксиметилцелюлози. Отримані результати свідчать про можливість регулювання гальмівного моменту гідрогальма змінюванням ексцентриситету між ротором і статором, які можна використати під час проектування гідравлічних гальм із регулювальним гальмівним моментом

Breast imaging technology: Application of magnetic resonance imaging to early detection of breast cancer

Since its first introduction approximately 10 years ago, there has been extensive progress in the application of magnetic resonance imaging (MRI) to the detection and diagnosis of breast cancer. Contrast-enhanced MRI has been shown to have value in the diagnostic work-up of women who present with mammogram or clinical abnormalities. In addition, it has been demonstrated that MRI can detect mammogram occult multifocal cancer in patients who present with unifocal disease. Advances in risk stratification and limitations in mammography have stimulated interest in the use of MRI to screen high-risk women for cancer. Several studies of MRI high-risk screening are ongoing. Preliminary results are encouraging