Calculation of Out‐of‐Plane Vibrations of a Porphin Molecule

Using the DFT/B3LYP method with the base set 631G^**, we carried out calculation of the frequencies of the normal vibrations of porphin and of its five isotopic types. Scaling of force constants for outofplane vibrations has been performed in independent natural coordinates. The symmetry coordinates are introduced and a force field for outof plane vibrations of a porphin molecule in independent coordinates of symmetry is obtained. A new correlation of the frequencies of vibrations in the type of the symmetry B _1u for the isotopic type of the d ₂ porphin molecule is suggested on the basis of discrete analysis of the distribution of a potential energy.     

Interpretation of Viscosity Behavior of a Polyelectrolyte in a Salt‐Free Polar Solvent by Ion‐Association

Abstract

On the basis of three hypothesis: (1) ion association according to the mass action law, (2) no interchain association due to the same sort of charges on the chains, and (3) chain expansion owing to intrachain Coulombic repulsive force, a theoretical equation was derived to describe the viscosity behavior of a polyelectrolyte in a salt‐free polar solvent. The resulting equation fits well with experimental viscosity behavior of a polyelectrolyte solution in polar solvents. With some approximations, the equation leads to the Fuoss empirical equation. The effects of molecular weight, the average distance of two neighboring ionizable groups along the polymer chain, and the nature of the solvent on the polyelectrolyte conformation are discussed.     

Conformational and Structural Analysis of 6‐(4‐Methoxy‐phenyl)‐1,5,7a‐triphenyl‐tetrahydro‐imidazo[1,5‐b][1,2,4]oxadiazol‐2‐one

Abstract

The cis stereochemistry of 6‐(4‐methoxy‐phenyl)‐1,5,7a‐triphenyl‐tetrahydro‐imidazo[1,5‐b][1,2,4]oxadiazol‐2‐one was studied by use of a PM3 semi‐empirical quantum mechanical model, and x‐ray crystallographic analysis. It crystallizes in the monoclinic space group P2 ₁ /n with a = 10.812(1) Å, b = 16.464(2) Å, c = 13.379(1) Å, α = 90.00°, β = 98.39(1)°, γ = 90.00°, V = 2356.07(4) Å³, Z = 4, D _calc = 1.3067 g cm^?3, F(0 0 0) = 976.41, and μ = 0.086 mm^?1. The structure was solved by direct methods and refined to R = 0.066 for 1257 independent reflections [I > 4σ (I)]. The results from x‐ray diffraction were seen to be generally consistent with the results from previously reported spectroscopic investigations, beside theoretical calculations, except for conformations of five‐membered fused heterocycles. Two inter‐ and intramolecular weak interactions in addition to carbon atoms (C1 and C3) with different chiralities were found in the structure. The conformational study was performed by randomly scanning the potential energy surface belonging to the title compound with respect to selected torsion angles.     

Temperature‐Triggered Capture of Dispersed Particles Using a Laponite‐Poly(NIPAM) Temperature‐Responsive Surface

In this study a new method is investigated that enables a conductive surface to be modified so as to capture dispersed particles when the temperature is increased. Poly(NIPAM) (NIPAM is N‐isopropylacrylamide) was grafted from electrodeposited Laponite RD particles using surface‐initiated atom transfer radical polymerization (ATRP) to give a temperature‐responsive surface. This was used to capture dispersed polystyrene particles. In the first part of the study the conditions used to electrodeposit Laponite onto a carbon foam electrode were determined. The ability of the temperature‐responsive surface to capture dispersed polystyrene particles was investigated between 20 and 50°C. Temperature‐triggered particle capture was reversible or irreversible depending on the conditions used during ATRP. A high surface concentration of poly(NIPAM) on the particle electrodes is believed to increase the extent of polystyrene particle capture and also reversibility. A theoretical analysis in terms of interaction energy–distance curves is presented for the capture behavior. It is concluded that the temperature‐responsive surface has both electrostatic and steric contributions to the total interaction energy. The steric component (which originates from poly(NIPAM)) is temperature‐dependent and provides the basis for temperature‐triggered particle capture.     

Influence of Close‐Range Dipole‐Dipole Interactions on the Real Part of the Susceptibility of a Dense Resonance Medium

Based on a solution of the stationary modified Bloch equations, an investigation is made of the influence of the effect of internal optical bistability (IOB) on the behavior of the refractive index of a dense resonance medium as a function of the constant b of closerange dipoledipole interactions, frequency detuning, and the intensity of optical radiation. The conditions of existence of the IOB effect of the system dense resonance medium + optical radiation are found and the dynamics of the loop width of the hysteresis dependence of the population difference of the resonance levels of the medium on the characteristics of the system is traced. The domains of the parameters are determined in which the effects of selffocusing and selfdefocusing of the radiation propagating in a dense resonance medium can take place.     

Investigation of the Melt‐Crystallization of Polypropylene by a Temperature Slope Method

Abstract

To investigate the in‐situ ordering process of isotactic polypropylene (iPP) from a melt state, a stationary growth front was prepared by the temperature slope crystallization (TSC) method. During the melt‐crystallization, iPP was crystallized into the α‐phase or β‐phase depending on the crystallizing conditions. The mechanism of the melt‐crystallization at the growth front was precisely observed by wide‐angle and small‐angle x‐ray scattering (WAXS and SAXS) using a strong synchrotron beam. In the TSC apparatus, the sample was crystallized in between a heater, controlled to 220°C, and a cooler, cooled by water to 25°C. We define the z‐axis parallel to the temperature gradient. A‐lamellae and B‐lamellae are also defined as those whose lamellar normal are perpendicular and parallel to the z‐axis, respectively. In a sample‐stop (SS) stage before the TSC, the original α‐phase lamellae became thicker, approaching to the melt‐solid boundary by annealing. The annealing process showed that the α‐phase B‐lamellae remained and the SAXS reflection was stronger on the meridian near the melt‐solid boundary in the SS stage. In the beginning of the TSC, the α‐phase B‐lamellae developed as a primary crystallization. During secondary crystallization under high supercooling, the SAXS cross pattern appeared showing that the α‐phase developed both A‐ and B‐lamellae. As the growth direction of A‐lamellae is parallel to the z‐axis, A‐lamellae grow faster than B‐lamellae. By the self‐epitaxial mechanism on the side surface of the A‐lamellae, the B‐lamellae grow on the base of the A‐lamellae. Following appearance of a spontaneous β‐nucleus, the β‐phase lamellae grew preferentially, excluding the α‐phase, and occupied the whole area of the sample. In this case also, A‐lamellae are advantageous to grow because of the growth direction parallel to the z‐axis. As a result, the SAXS β‐phase reflection appeared on the equator.     

Mechanism of Intramolecular Transfer of a Proton and an Electron in an Excited State of 4′‐Amine Derivatives of 3‐Hydroxyflavone

The intramolecular transfer of a proton in 4amine derivatives of 3hydroxyflavone was investigated in binary solvents, which are a mixture of polar and nonpolar liquids. The dependence of the efficiency of the intramolecular transfer of a proton in an excited state on the frequency of the exciting light has been revealed, which is due to the spectral inhomogeneity of the molecules of fluorophors in binary solvents. A scheme of the processes of intramolecular transfer of a proton and an electron in 4amine derivatives of 3hydroxyflavone is suggested.     

Radiative Properties of an SHF Discharge Formed by a Ring‐Type Waveguide‐Slot Radiator

The actual spatial distribution of the intensity of SHF discharge glow in oxygen at different distances from the zone of input of SHF power has been investigated by the method of optical emission spectroscopy with subsequent abelization of the experimentally obtained integral characteristics of the intensity of radiation emitted by the OI ( = 777.7 nm) line. The investigations were carried out in a plasmatron on the basis of a ringtype waveguideslot radiator. The experimental results obtained indicate that the best uniformity of optical radiation over the discharge length is attained in the mode of pressureoptimum gas breakdown. Radial distributions of the radiation intensity are complicated in nature, which can be attributed to the differently pronounced skin effect exerted by a plasma on an electromagnetic wave under different discharge conditions. The results of the present work make it possible to interpret the previously obtained data of technological experiments and can be employed in developing technological processes of SHF plasma processing of materials and in designing SHF plasmatrons.     

Spectral‐Luminescence and Generation Properties of 1‐Aza‐2‐Methyl‐6‐Aminopyrene and of Its Protolytic Forms

Spectral manifestations of protolytic forms of 1aza2methyl6aminopyrene in ethanol and aqueous solutions are investigated. The ionization constants of the protolytic forms are determined. The generation properties and photostability of a neutral molecule and a cation in excitation by an excimer XeCl laser are studied.     

Formation Dynamics of Absorbing Layers in a Two‐Stage Atomizer

An experimental spatialresolution facility for recording the formation dynamics of absorbing layers in a twostage atomizer is described. An optical scheme with a convergent raying beam in the atomizer zone and a hollow cathode as a radiation source is considered. The dynamics of the absorptivity signal at evaporation of Rb, NaCl, and a standard sample CASS2 has been investigated under different operating conditions of the atomizer. It is shown that the proposed evaporation–condensation–atomization regime considerably lowers the spatial gradients of absorptivity and the level of nonselective absorption in recording the atomic absorption signal.     

Initiation of Light Pulses by a Coaxial H‐Compressed Discharge

An optimum configuration of the discharge channel of a coaxial Hcompressed discharge is determined to exclude the screening influence of an envelope on discharge radiation in the UV region of a spectrum. It is shown that the use of an Hcompressed discharge of coaxial shape makes it possible to increase the radiation yield in the UV spectrum as compared to a plane shape at the same parameters of electric power supply.     

Segregation of Components as a Result of High‐Power Laser Irradiation of Heterogeneous Condensed Media

The effects of periodic segregation of components in metastable (supercooled or supersaturated) binary alloys in the course of kinetic phase transformations as a result of laser irradiation of heterogeneous systems were studied analytically. Nonlinear processes of temporal and spatial selforganization of concentrationrelated structures were simulated using (i) a selfconsistent system of timedependent twodimensional equations for the distribution function for the sizes and spatial coordinates of the newphase particles and (ii) balance equations for the temperature and concentration of dissolved components; the latter equations account for nonlinearity of the particlesource function, sinks, for dependences of the phasetransition temperature on the surface curvature of particles and on the concentration of components, and for diffusive motion of particles in space. The domain of existence for the instabilities under consideration and the characteristics of the formed crystallizationrelated periodic structures are determined. It is established that nanoclusters formed during supersaturation of crystallizing material may play an important role in generation of selfoscillatory crystallization modes. Hydrodynamic aspects of liquidphase concentrationrelated stratification in heterogeneous systems based on immiscible components are considered.     

Theoretical and Experimental Study of the Conformation and Vibrational Frequencies of N‐Acetyl‐L‐alanine and N‐Acetyl‐L‐alaninate

The vibrational frequencies of N‐acetyl‐L‐alanine (NAAL), its potassium salt (NAALK) and its free anionic form (NAAL^?) are calculated using density functional theory (B3LYP) combined with the 6‐311 + + G(d,p) basis set. The experimental Raman spectrum of solid NAALK and the scaling factors for calculated values are discussed as well. The three species are characterized by intramolecular NH…O hydrogen bonds leading to the formation of a five‐membered ring. As indicated by the intramolecular (N)H…O distances and by the ν(NH) frequencies, the strength of the intramolecular hydrogen bond is ordered as follows: NAAL^? < NAALK < NAAL^?. Owing to their difference in the coupling with other vibrational modes, the in‐plane and out‐of‐plane vibrations do not reflect the strength of the hydrogen bond.     

Crystal Structures of Tetrakis‐(4‐chlorophenylthio)‐butatriene and Tetrakis‐(tert‐butylthio)‐butatriene

Tetrakis‐(4‐chlorophenylthio)‐butatriene (3a) and tetrakis‐(tert‐butylthio)‐butatriene (3b) were synthesized, and their crystal structures were determined. The compound 3a is monoclinic, space group P2₁/c, a=6.9785(8), b=8.6803(9), c=22.884(2) Å, β=93.887(6)^o, V=1383.0(3) ų, Z=2. The compound 3b is monoclinic, space group P2₁/n, a=11.0615(6), b=10.8507(4), c=11.2717(6) Å, β =116.427(2)^o, V=1211.5(1) ų, Z=4. The title compounds 3a and 3b reside on an inversion center so that only half of the molecule is crystallographically unique. Both compounds are not planar. The crystal structures of 3a and 3b have cumulated double bonds. The C7–C8–C8ⁱ and C5–C6–C6ⁱ angles that show the linearity in both structures, respectively, are 176.4(3)° in 3a and 175.6(2)° in 3b.     

Rheological Behavior of Polyarylsulfone 1‐Butyl‐3‐Methylimidazolium Chloride Solutions

Polyarylsufone polymers are engineering thermoplastics that can only be dissolved in polar solvents. We found that polyarylsufone has good solubility in ionic liquid (IL) with IL being a new kind of green solvent; thus, ILs are potential substitutes for conventional molecular solvents. However, the thermodynamics in ionic liquids are different then those in conventional solvents, so ILs as solvents have attracted enormous attention recently. Rheological behavior is an important factor in polymer material processing. The rheological behavior of polyarylsulfone (PASF) in both N, N,‐dimethylacetamide (DMAc) and ionic liquid 1‐butyl‐3‐methylimidazolium chloride [(Bmim) Cl] were studied in this paper as a function of concentration for concentrated solutions. It is interesting that the rheological behavior of the PASF/(Bmim) Cl solution is very different from that of PASF/DMAc solutions. In DMAc, as concentration increases viscosity increases, while the rheological behavior of the PASF/(Bmim) Cl solution exhibits a maximum in the viscosity‐concentration plots.     

Fine‐Structure Fluorescence Spectrum of a Dication Form of Porphin in an Inorganic Gel Matrix

It is shown that the molecules of the free base of porphin (H₂P) incorporated into an inorganic tetraethoxysilane (TEOS) gel matrix produce a dication form H₄P²⁺. A finestructure spectrum of the fluorescence of H₄P²⁺ is obtained at 4.2 K on selective photoexcitation. A conclusion on the manifestation of the outofplane vibrations of the porphyrin macrocycle in the lowfrequency region of the vibronic spectrum of porphin dication is drawn and the assignments of the corresponding frequencies to the vibrations of a certain form are suggested.     

Electroluminescence and Spectral Properties of N9‐Isobutyl‐2‐Oxo‐3‐Phenyl‐3N‐Benzo[F]Chromene‐9‐Sulfonamide

Experimental data on the synthesis and spectral properties (UV, IRFourier, xray photoelectronic, and luminescence spectra) of the sulfonamide derivative of benzocoumarin in an isopropanol solution and in a film applied by thermal vacuum deposition (TVD film) are reported. The use of TVD films of the investigated substance as electroluminophors is shown to be promising.     

Excitation Mechanisms of Copper Ionic and Atomic Lines Emitted from a Low‐Pressure Argon Laser‐Induced Plasma

Abstract

Low‐pressure laser‐induced plasmas generated with a pulsed Nd∶YAG laser have complicated structures both temporally and spatially. The emission characteristics of the plasma are investigated for optimizing the experimental parameters in atomic emission spectrometry. The emission intensities of copper emission lines, measured in a time‐resolved as well as a time‐integrated mode, are strongly dependent on the kind of copper lines, ionic or atomic line, and the excitation energy. Also, the pressure of argon gas is the most important parameter for determining the behavior of these emission lines, including argon lines. Generally, copper ionic lines are dominantly emitted from the initial breakdown zone, because the copper ions are produced mainly in the hot breakdown zone. However, the Cu II 229.44‐nm line is emitted also from the expansion zone of the plasma. It results from an additional excitation process through the charge‐transfer collision particularly effective for the corresponding excited level. In this work, the excitation mechanisms for Cu I, Ar I, and Ar II lines are also discussed. The excitations occurring in the laser‐induced plasma can be well understood by taking the temporal and spatial variations in their intensities into consideration.     

Structural Characterization of RF‐Sputtered a‐C:N Thin Films by Raman,IR, and X‐ray Reflectometry Spectroscopies

Abstract

Amorphous carbon nitride thin films (a‐C:N) were deposited from a carbon target, at room temperature onto silicon substrates, by reactive RF sputtering in a gas mixture of argon and nitrogen. The structural properties of these films have been studied by Raman, infrared (IR), and X‐ray reflectometry spectroscopies. Both the IR and Raman spectra of the a‐C:N films reveal the presence of C–C, C?C, C?N, and C≡N bonding types. The Raman spectra analysis shows, an increase of the C≡N triple bonds content when the concentration of nitrogen C(N₂) in the gas mixture is increased. The Raman intensities ratio between the disorder (D) and graphitic (G) bands increases with C(N₂) suggesting an increased disorder with the incorporation of nitrogen in the carbon matrix. The effect of C(N₂) on the density of a‐C:N films was also investigated by X‐ray reflectometry measurement. The increase of the nitrogen concentration C(N₂) was found to have a significant effect on the density of the films: as C(N₂) increases from 0 to 100%, the density of the a‐C:N films decreases slightly from 1.81 to 1.62 g/cm³. The low values of density of the a‐C:N films were related (i) to the absence of C–N single bonds, (ii) to the increase of disorder introduced by the incorporation of nitrogen in the carbon matrix, and (iii) to the presence of the bands around 2350 cm^?1 and 3400 cm^?1 associated with the C–O bond stretching modes and the O–H vibration, respectively, suggesting a high atmospheric contamination by oxygen and water. The presence of these bands suggests the porous character of the studied samples.     

Spectral Analysis of a Hardening Medium Based on I‐20A Oil

Chemical conversions occurring in a hardening medium based on I20A mineral oil through its servicelife are investigated by spectroscopy methods in the IR, visible, and UV regions and by luminescence, massspectroscopy, and elemental analysis methods. The possible reasons leading to deterioration of its cooling properties are established. IR spectroscopic techniques of quantitative determination of the content of compounds in a hardening medium that negatively and positively influence its cooling ability are suggested.