Time-resolved fluorescence studies of ribonuclease T1 in reversed micelles

Time-resolved fluorescence intensity and anisotropy decay data were obtained for ribonuclease T₁ entrapped in bis(2-ethylhexyl) sodium sulfosuccinate/heptane reverse micelles, as a function of the size of the inner water pool at neutral pH. Data have been presented previously to show that this protein retains its native structure and undergoes reversible thermal unfolding in these reverse micelles (Shastry and Eftink,Biochemistry 36, in press). The fluorescence decay of entrapped protein is similar to that for the protein in buffer. The rotational correlation time of entrapped ribonuclease T₁ is found to be longer than that in buffer; this rotational correlation time decreases with increasing size of the water pool but is still over twice the value for the protein in buffer for the largest size of water pool investigated, indicating an increased microviscosity within the reverse micelle. Thermal unfolding of the protein results in a significant decrease in the rotational correlation time of the entrapped proteins, consistent with the protein being unfolded but not interacting with the inner surfactant wall of the reverse micelle.Nomenclature _i Amplitude of component i associated with fluorescence decay _i - _i Fractional intensity associated with fluorescence decay time _i - Rotational correlation time g_i Amplitude of component i associated with anisotropy decay _i - _max Fluorescence emission maximum - r_o Fundamental anisotropy of an immobilized fluorophore - _i Fluorescence lifetime of component i - W_o Ratio of water molecules per detergent molecules in a reverse micelle     

Rotational and vibrational temperatures measured in a chemiluminescent flame from FTIR Bi2 emission spectra

Rotational and vibrational temperatures of the Bi₂ dimer have been measured in a chemiluminescent flame. Emission spectra of the Bi₂ a³Σ_u⁺(a₁1_u)→X¹Σ_g⁺(X0_g⁺) transition in the near-infrared region were recorded with a FTIR spectrometer. High-resolution spectra of the 0-3, 0-8, 0-9, 2-3, 4-1, 6-0, 6-1, and 7-1 bands served for the determination of the rotational temperature. It was observed that both rotational and vibrational levels are described well by Boltzmann distributions. The average rotational temperature was found to be consistent with the vibrational temperature . The study has shown that such a very heavy molecule as Bi₂ can serve for temperature measurements by optical emission as reported so far only for light molecules.     

High spin band structures in104Cd

High spin states in¹⁰⁴Cd have been investigated by means of heavy ion induced reactions using the Nordball detector array. The level scheme constructed from -coincidences is dominated by three band structures. The positive parity band shows no rotational like energy spacing. It is thus understood mostly in terms of quasiparticle excitations with vd_5/2, vg_7/2 andg_9/2 configurations. The collective properties of the negative parity bands are more pronounced. These bands are most likely due to v(h_11/2,d_5/2) and v(h_11/2,g_7/2) structures.     

Spectral‐Luminescent Properties of 1,1‐Dioctadecyl‐3,3,3'3'‐Tetramethylindodicarbocyanineperchlorate in Binary Solutions

On the basis of investigation of the absorption and luminescence spectra of 1,1dioctadecyl3,3,3'3'tetramethylindodicarbocyanineperchlorate (D307) molecules and their nonamphiphilic analog in binary solutions of dimethylformamide and water of different composition, a mechanism underlying the quenching luminescence of the D307 molecules has been established which is related to the formation of nonluminescent associates. It is shown that the formation of the micelles of sodium dodecylsulfate (SDS) in a binary solution with 99% content of water destroys the associates, the D307 molecules are captured by the micelles, and their mobility in the micelles is limited.     

Absorption spectra of AsH2 radical in 435-510 nm by cavity ringdown spectroscopy

The absorption spectra of jet-cooled AsH₂ radicals were recorded in the wavelength range of 435-510 nm by cavity ringdown spectroscopy. The AsH₂ radicals were produced by pulsed DC discharge in a molecular beam of a mixture of AsH₃, SF₆, and argon. Seven vibronic bands with fine rotational structures have been identified and assigned as the , , and (n = 1-3) bands of the electronic transition. Based on the previous studies of AsH₂ radical, rotational assignments and rotational term values for each band were obtained, and the molecular parameters including vibrational constants, rotational constants, centrifugal distortion constants, and spin-rotation interaction constants were also determined.     

Longitudinal rf discharge in Xe/Cl<Subscript>2</Subscript> mixtures

Results are presented from the studies of the electrical and emission characteristics of the low-temperature plasma of a longitudinal rf (f₀=1.76 MHz) discharge in Xe/Cl₂ mixtures at pressures of 100–800 Pa. The discharge was ignited in a cylindrical quartz tube with an inner diameter of 1.4 cm and interelectrode distance of 3.0 cm. The discharge emission within the spectral range of 190–670 nm is studied. The dynamics of the discharge current and discharge emission at different pressures and compositions of a Xe/Cl₂ mixture are investigated. It is shown that a discharge in a Xe/Cl₂ mixture acts as a wideband excimer-halogen lamp with a cylindrical output aperture emitting in the spectral range of 220–320 nm. The broad plasma emission spectrum is formed due to the overlap of the XeCl(D, B-X; B, C-A) bands that are broadened at low working-gas pressures. The composition of the working mixture is optimized to achieve the maximum power of the wideband UV plasma emission. Longitudinal rf discharges in low-pressure Xe/Cl₂ mixtures are of interest for developing small-size wideband (Δλ=220–450 nm) cylindrical-aperture lamps, whose efficiency can, on average, exceed the efficiency of conventional hydrogen lamps by more than one order of magnitude.     

Spectroscopic diagnostics of barrier discharge plasmas in mixtures of zinc diiodide with inert gases

The spectral characteristics of the emission of gas discharge atmospheric pressure plasmas in mixtures of zinc diiodide vapor with inert gases (He, Ne, Ar, Kr, and Xe) are investigated. The formation of a gas discharge plasma and the excitation of the components of a working mixture were performed in a high-frequency (with a repetition frequency of sinusoidal voltage pulses of 100 kHz) barrier discharge. The gas discharge emission was analyzed in the spectral range 200–900 nm with a resolution of 0.05 nm. Emission bands of ZnI(B-X) exciplex molecules and I₂* excimer molecules, lines of inert gases, and emission bands of XeI* exciplex molecules (in Xe-containing mixtures) were revealed. It is ascertained that the strongest emission of ZnI* molecules is observed in ZnI₂/He(Ne) mixtures. The regularities in the spectral characteristics of the gas discharge plasma emission are considered.     

Preferential Solvation of 1,4-Dimethoxy-2,3-Dimethyl-9,10-Anthraquinone-A Spectrophotometric and Fluorometric Study

Electronic absorption and fluorescence emission spectra of DMDMAQ (1,4-dimethoxy-2,3-dimethyl-9,10-anthraquinone) have been studied as a function of solvent composition in some binary mixtures and in different neat solvents. The binary mixtures consist CCl₄ (Carbon tetrachloride)-DMSO (Dimethylsulfoxide), EtOH (Ethanol)-DMSO, and CCl₄-EtOH combination of single solvents. The wavelength maxima of the absorption band for DMDMAQ are quite solvent sensitive in aprotic solvents. But, in protic solvent, there is no marked shift in absorption and emission maximum which shows the absence of specific interaction. Excited state shows increasing shift with increasing solvent polarity compared to ground state. The ratio of dipole moment in the excited state to that in the ground state was calculated. Different criteria were considered to analyse preferential solvation characteristics in different binary mixtures, viz., local mole fraction (), solvation index (δ_S2) and exchange constant (K₁₂).     

Infrared emission spectroscopy and ab initio calculations on VCl

The emission spectrum of VCl has been investigated at high resolution in the 3000-19 400 cm⁻¹ region using a Fourier transform spectrometer. The bands were excited in a high temperature carbon tube furnace by the reaction of vanadium metal vapor and a trace of BCl₃ as well as in a microwave discharge lamp by the reaction of VOCl₃ vapor with active nitrogen. The spectra were recorded using the Fourier transform spectrometer associated with the McMath-Pierce telescope of the National Solar Observatory at Kitt Peak. The analysis of the system of VCl (previously labeled as ) has been extended by analyzing the rotational structure of some additional bands. A rotational analysis of the , , and subbands of the 0-2, 0-1, 0-0, and 1-0 bands, and the subband of the 0-1 and 0-0 bands has been obtained and molecular constants have been extracted. The subband was not identified in any of the assigned bands. The spectroscopic properties of the low-lying electronic states of VCl have been predicted by CASSCF/CMRCI ab initio calculations and the experimental assignments are supported by the ab initio results.     

The effect of ligand field on the excitation luminescence spectra of some complex compounds of manganese (II)

The excitation and emission luminescence spectra of the complex compounds of manganese (II) chloride with the hydrochlorides of pyridine, 2-methyl- and 2-ethylpiperidine have been studied. It has been established that the crystals of these complex compounds appear in tetrahedral and octahedral configurations. The excitation spectra in both configurations contain bands originating from the⁴G,⁴P,⁴D and⁴F terms, the position of which is determined by configuration. From the excitation spectra the Racah parametersB andC and the ligand field strength parameter 10Dq have been determined.The emission luminescence spectra also depend on configuration of the complex compound. The character of these spectra is expressed in terms of the following characteristic parameters: the position of the maximum of the functionG(v), the half-width of the emission luminescence band, and the constants andm. From the excitation and emission luminescence spectra it has been established that the emission in both configurations is due to the⁴T₁(G)⁶A₁ transition.     

Luminescence in the systems ZnS-CuAlS2 and ZnS-AgAlS2

ZnS-CuAlS₂ and ZnS-AgAlS₂ phosphors (denoted by CuAl and AgAl) have blue, green, and red emission bands. The excitation spectra of these bands have characteristic peaks. The effects of activator concentration on the parameters of the emission and excitation spectra are examined.     

New combination bands in CCH2 around 0.83 μm recorded using FT-ICLAS

Fourier-transform intracavity laser absorption spectroscopy allowed five ¹²C¹³CH₂ Σ⁺-Σ⁺ bands, all from the ground state, to be identified in the 0.83 μm range. Their rotational analysis was performed and rotational constants are provided. Three of these bands, with origins at 11616.9684(18), 11737.2356(14), and 11761.0322(23) cm⁻¹, have never been reported before. Their upper states are assigned to , respectively.     

Observation of new laser transitions and saturation effects in optically pumped NO

We report investigations of an NO laser employing specially profiled magnetic fields of up to 3.4T, and F₂ pump laser intensities as great as 20 MW cm^–2. We have observed laser oscillation at 226 nm on a rotational branch of the B'-X/it(3–11) band of NO for the first time, in addition to the previously reported oscillation at 218 nm on the B'-X/it(3–10) band. We have also observed visible laser emission on a rotational branch of the B ²-B ² II(3–1) band of NO. Saturation of the NO laser pulse energy with pump intensity has been observed, the total NO laser pulse energy having been increased to 490 J. The possibility of increasing the NO laser pulse energy towards 1 mJ per transition is discussed.     

Rotational quantum analysis of the orange bands of the Ca2 molecule

An analysis of the rotational structure of the '-' system of orange bands for the Ca₂ molecule (5900–6200 Å) is performed.     

The effect of an external magnetic field on the L subshell X-ray fluorescence cross sections and L subshell fluorescence yields in elements 73 ≤ Z ≤ 92 by 59.54 keV photons

L_i (i = 1, 2 and 3) X-ray fluorescence cross sections for Ta, W, Au, Hg, Tl, Pb, Bi, Th and U have been measured using the 59.54 keV incident photons energy in the external magnetic field of intensity +0.60 T. The values of L_i subshell fluorescence yields (w₁$w_1$, w₂$w_2$ and w₃$w_3$) have been measured for the same elements using the previously measured cross section values and the theoretical L_i subshell photoionisation cross sections, Coster–Kronig transition probabilities and emission rates. It is observed that the measured L_i subshell X-ray fluorescence cross section and L_i subshell fluorescence yield values for B = 0 are in good agreement with the theoretical ones evaluated using L_i subshell fluorescence yield and L_i subshell photoionization cross section. Furthermore, the results show that the atomic parameters such as spectral linewidth, radiation rates, photoionization cross section and fluorescence yield can change when the irradiation is conducted in a magnetic field.     

Mechanical instabilities of bubble clusters between parallel walls

We have carried out a systematic study of buckling-like mechanical instabilities in simple two- (2D) and three-dimensional (3D) symmetric foam clusters sandwiched between parallel planar walls. These instabilities occur when the wall separation w is reduced below a critical value, w^*, for which the foam surface energy E reaches its minimum, E^*. The clusters under investigation consist of either a single bubble, or of twin bubbles of fixed equal sizes (areas A in 2D or volumes V in 3D), which are either free to slide or pinned at the confining walls. We have numerically obtained w^* for both free and pinned 2D and 3D clusters. Furthermore, we have calculated the buckled configurations of 2D twin bubbles, either free or pinned, and of 3D free twin bubbles, whose energy is independent of w and equal to the minimum energy E^* of the unbuckled state. Finally, we have also predicted the critical w_t^* at which the terminal configurations under extension of 2D and 3D single and twin bubbles are realised. Experimental illustrations of these transitions under compression and extension are presented. Our results, together with others from the literature, suggest that a bubble cluster bounded by two parallel walls is stable only if the normal force it exerts on the walls is attractive, i.e., if dE/dw > 0; clusters that cause repulsion between the walls are unstable. We correlate this with the distribution of film orientations: films in a stable cluster cannot be too parallel to the confining walls; rather, their average tilt must be larger than for a random distribution of film orientations.     

Pressure broadening coefficients of the water vapor lines at 556.936 and 752.033 GHz

The air induced broadening coefficients of the pure rotational transitions of H₂O at 556.936 GHz (1₁₀←1₀₁), and 752.033 GHz (2₁₁←2₀₂) were measured by terahertz time-domain spectroscopy. The air broadening coefficient was determined to be for the 556.936 GHz line and for the 752.033 GHz line, respectively. The present broadening coefficients for the 556.936 GHz water line are significantly smaller than those of Markov and Krupnov [Measurements of the pressure shift of the 1(10)-1(01) water line at 556.936 GHz produced by mixtures of gases. J Mol Spect 1995:172;211-4] but relatively close to the values of the HITRAN database. The measured data may improve the accuracy of the abundance of water vapor retrieved from spectra obtained by the Odin/SMR satellite instrument. The effect on the satellite retrieval processing is discussed.     

The wetting transition in a random surface model

We continue our analysis of the phase diagram of a discrete random surface, with no downward fingers, lying above a flat two-dimensional substrate. The surface is closely related to the 2D Ising model and its free energy is exactly solvable in much (but not all) of the phase diagram. There is a transition at temperatureT _w from a high-T infinite height or wet phase to a low-T finite height or partially wet phase. Previously it was shown that when a parameterb, related to the contact interaction, is positive,T _w is independent ofb and there is a logarithmic specific heat divergence asT _w is approached fromeither side. Here we show that forb<0,T _w does depend onb and there isno thermodynamic singularity from the wet phase. The partially wet phases forb0 andb>0 differ in the absence or presence of a monolayer covering the entire substrate; this results in a first-order transition across the lineb=0,T<T _w.This paper is dedicated to Jerry Percus.     

Multiwave Low‐Pressure Excimer Radiator

The excitation conditions and characteristics of a longitudinal glow discharge in a short tube of small diameter in Kr/Cl₂ and Ar/Kr/Cl₂ mixtures are investigated. It is shown that this discharge is a multiwave radiation source on systems of the 199/222/258 and 175/199/222/258 nm bands. Optimization of the pressure and composition of working mixtures most applicable for obtaining the approximately equal intensity of the ArCl(B X), KrCl(D, B X), and Cl₂(DA) radiation bands is carried out in the discharge investigated. A multiwave UVVUV radiation source is of interest for use in photometry, microelectronics, photochemistry, and medicine.     

The luminescence of unactivated alkali iodides

Two shorter wave-length emission bands have been observed in activated alkali iodides at — and light excitation apart from activator emission. The shortest wave-length band, observed only at low temperatures, is excited in exciton absorption bands and it may be due to exciton emission.This emission has greater intensity in unactivated crystals grown from the solution. We have observed this emission on CsI, KI and RbI crystals.The intermediate emission band is excited in a narrow excitation band, situated on the sharp slope of the fundamental absorption in crystals and it can apparently be ascribed to structural defects.We wish to thank M. D. Galanin for interest in this work and L. M. amovski for providing us with crystals.