13CH3OH and13CD3OH optically pumped fir laser: New large offset emission and optoacoustic spectroscopy

27 new, large offset, FIR laser lines from¹³CH₃OH and one from¹³CD₃OH have been discovered by pumping with a high tunability waveguide CW CO₂ laser. Optoacoustic measurements of isotopic methyl alcohol have also been performed and the pump offsets of the new and of previously known lines have been measured and checked. Frequency tunability by Stark effect has been observed for 6 strong lines. Some assignments are discussed.     

A Sensitive and Precise Method for Estimation of Free Thyroxine in Serum as a Thyroid Function Test Using L-Thyroxine-125I

A method for free thyroxine estimation in serum, using labelled thyroxine and Sephadex G-25 has been developed.

The experiment has been carried out by incubating labelled thyroxine with serum samples and separating the free thyroxine from bound protein in the serum by gel filtration after complete equilibrium between exogenous and endogenous thyroxine. Factors affecting the free thyroxine ratio such as volume of serum used, concentration of labelled thyroxine, time and temperature of incubation were studied and the optimum conditions for the test were selected.

The sensitivity of the technique was determined by carrying out twelve estimations of the free thyroxine ratio on samples of pooled normal serum, pooled hypothyroid serum, and pooled hyperthyroid semm. In addition free thyroxine ratio leas determined for 23 hypothyroidisms, 99 euthyroid patients, 40 untreated thyrotoxicosis and 50 normal serum samples. A good correlation with the thyroid status of the patients (as determined) clinically and with radioiodine techniques was observed.     

Levels in74As from the74Ge(p,nγe)74As reaction

The low-lying levels in⁷⁴As have been studied by means ofγ-ray and internal conversion electron spectroscopy following the⁷⁴Ge(p,n)⁷⁴As reaction. New levels at 372.7, 532.8, 632.1, 731.6, 752.7, 758.3, 801.6, 902.9 and 1128.5 keV, not observed in earlier studies, have been established.J ^π assignments have been made to several low-lying levels. An earlier ambiguity regarding the identification of an isomeric level has been clarified. The half-life of a level at 271.4 keV has been measured to be 1.0±0.1 nsec; in addition, limits on half-lives of levels at 182.7, 277.5 and 425.4 keV have been assigned. The level structure is discussed on the basis of available nuclear models.     

Crystal fields of Pr in LiYF4 under pressure

Fluorescence spectra of LiYF₄:Pr³⁺ have been measured between 12,000 and 22,000 cm⁻¹ under pressures up to 10 GPa. In total, 25 crystal field energy levels were obtained and used for the determination of free-ion and crystal field parameters under pressure. According to the nephelauxetic effect, the free-ion parameters decrease with increasing pressure. The relative decrease is larger for the Slater than for the spin-orbit coupling parameter. This behavior is consistent with former studies on Pr³⁺ in different crystals and can be explained by a special covalency model. According to an effective D_2d symmetry, five crystal field parameters B₀²(f,f), B₀⁴(f,f), B₄⁴(f,f), B₀⁶(f,f), and B₄⁶(f,f) are non-zero. The pressure-induced changes of these parameters have been determined up to the maximum pressure of 10 GPa. In order to improve the calculation of the crystal field levels, the configuration interactions with the 4f¹6p¹ configuration have been taken into account. The effect of these interactions are also analyzed under pressure and distinct improvements of the energy level calculations have been obtained.     

Specific features of photo and thermoluminescence of Tb ions in BaO-M2O3 (M=Ga, Al, In)-P2O5 glasses

BaO-P₂O₅ glasses mixed with the three metal oxides viz., Al₂O₃, Ga₂O₃ and In₂O₃ doped with Tb₂O₃ were prepared. The glasses were characterized by X-ray diffraction and differential thermal analysis. Optical absorption and photoluminescence spectra and thermoluminescence (TL) of these glasses have been studied. From the measured intensities of various absorption bands of these glasses, the Judd-Ofelt parameters Ω₂, Ω₄ and Ω₆ have been evaluated and compared with those of other reported glass systems. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of these glasses. From this theory various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r and the emission cross-section σ^E for various emission levels of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies of all the three glasses. The analysis of TL data indicate high non-radiative losses in In₂O₃ mixed glasses.     

Fluorescence features of Sm ions in Na2SO4-MO-P2O5 glass system—Influence of modifier oxide

Na₂SO₄-P₂O₅:Sm³⁺ glasses mixed with three different alkaline earth modifier oxides viz., MgO, CaO and BaO were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature; the Judd-Ofelt theory was successfully applied to characterize these spectra. From this theory, various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r, for various emission levels in the spectra of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies in the change of scenario for modifying oxides in the glass network.     

Luminescence of La3F3[Si3O9]:Ce

The luminescence properties of Ce³⁺ in La₃F₃[Si₃O₉] are reported. Excitation and emission bands corresponding to 4f¹→5d¹ transitions of Ce³⁺ were identified. The center of gravity of the 5d states lies at remarkable high energy (43.2×10³ cm⁻¹) for Ce³⁺ in a silicate compound. This high value is attributed to the combined oxygen/fluoride coordination of the Ce³⁺ ion. Emission from the lowest 4f5d level to the ²F_5/2 and ²F_7/2 levels was found at 32.4×10³ and 30.4×10³ cm⁻¹. These results are compared with literature data on silicates and fluorides. From the values found for Ce³⁺, predictions are made for the positions of the 4f5d bands of Pr³⁺ and Er³⁺ in La₃F₃[Si₃O₉]. For both ions, it is concluded that in this host lattice emission is expected from high lying 4fⁿ energy levels.     

Studies on the Purity of 51Cr Labelled Human Serum Albumin

Different methods reported for the purification of Chromium-51 labelled human serum albumin have been studied in detail. It has been found that purification by ion exchange or dialysis does not remove some of the impurities such as complexed chromium and hydrated chromic oxide. Purification over DEAE cellulose or Sephadex (A-50) gives a product which is free from these impurities. It has been confirmed that chromium labelling leads to the formation of labelled protein aggregates and the specific activity of the labelled aggregates is greater than that of the non-aggregated fraction. These aggregates can be separated from the labelled monomer by column chromatography of Gel filtration.     

TeO2-ZnO-Na2O-K2O玻璃中Er3+离子掺杂浓度对其发光及荧光寿命的影响

测量了不同掺杂浓度下Er³⁺离子在碲酸盐玻璃中的吸收光谱、发射光谱和Er3+离子的荧光寿命，计算了Er³⁺离子的发射截面σ_e,分析 了Er ³⁺离子掺杂浓度对其发光强度和荧光寿命的影响.结果表明，Er³⁺离子掺 杂浓度较低时，对其荧光强度和荧光寿命没有显著的影响；掺杂浓度高时，出现了浓度猝灭 效应，使Er³⁺离 子荧光光强度降低，荧光寿命下降.实验确定了掺杂浓度最优值，同时对浓度猝灭机制进行 了分析. 关键词： 碲锌碱玻璃 3+离子')" href="#">Er³⁺离子 掺杂浓度 发光和荧光寿命     

Ag concentration dependent transport properties of LiF-MoO3-P2O5 glasses

LiF-MoO₃-P₂O₅ glasses mixed with different concentrations of Ag₂O (ranging from 0 to 1.0 mol%) was prepared. D.C. conductivity and dielectric properties over a range of temperature have been investigated. The analysis of the results of d.c. conductivity has indicated that T>θ_D/2, the small polaron hoping model seems to be fit and the conduction is adiabatic in nature. These results further indicated that there is a change over of conduction mechanism from electronic to ionic at about 0.4 mol% of Ag₂O. The low temperature part of a.c. conductivity is explained based on quantum mechanical tunneling model. The quantitative analysis of these results is further extended with the aid of the data on optical absorption, ESR and IR spectral studies.     

Reinvestigation of the second negative (A 2 Π u−X 2 Π g) band system of O 2 +

TheA ² Π _ustate of O₂ ⁺ was earlier established as an inverted state contrary to previous assumptions. The rotational analysis of a few more bands of theA-X system of O₂ ⁺ has now been completed. These studies show that the spin-orbit coupling constantA in theA ² Π _ustate gradually varies with the vibrational quantum numberν and is found to be positive forν⩾6. It has also been observed that the spia-rotation interaction is not negligible in theA ² Π _ustate. The spin splitting constantγ is reported for various vibrational levels of this electronic state.     

The influence of Pr co-doping on the luminescent properties of Lu2O3:5 mol% Eu films

Uniform and crack free polycrystalline lutetium oxide (Lu₂O₃:(Eu,Pr)) films were fabricated by Pechini sol-gel method combined with the spin-coating technique. X-ray diffraction (XRD) and atomic force microscope (AFM) characterizations indicated that the obtained film was composed of polycrystalline cubic Lu₂O₃ phase with an average grain size around 30 nm. The photoluminescence(PL) spectra and decay performances of the Lu₂O₃:5 mol% Eu films co-doped by 0-0.5 mol% Pr³⁺ with different concentrations were characterized. It was found that the afterglow was reduced obviously due to the introduction of 0-0.5 mol% Pr³⁺ in the Lu₂O₃:5 mol% Eu films coupled by decrease in the emission intensity at 612 nm. The mechanism of afterglow diminishing was discussed based on the thermoluminescence measurements.     

The molecular structure and the analytical potential energy function of S2^- and S3^-

In this paper, the equilibrium geometry, harmonic frequency and dissociation energy of S2^- and S3^- have been calculated at QCISD/6-311＋＋G（3d2f） and B3P86/6-311＋＋G（3d2f） level. The S2^- ground state is of 2IIg, the S3^- ground state is of 2B1 and S3^- has a bent （C2v） structure with an angle of 115.65° The results are in good agreement with these reported in other literature. For S3^- ion, the vibration frequencies and the force constants have also been calculated. Base on the general principles of microscopic reversibility, the dissociation limits has been deduced. The Murrell-Sorbie potential energy function for S2^- has been derived according to the ab initio data through the least- squares fitting. The force constants and spectroscopic data for S2^- have been calculated, then compared with other theoretical data. The analytical potential energy function of S3^- have been obtained based on the many-body expansion theory. The structure and energy can correctly reappear on the potential surface.     

MARVEL: measured active rotational-vibrational energy levels

An algorithm is proposed, based principally on an earlier proposition of Flaud and co-workers [Mol. Phys. 32 (1976) 499], that inverts the information contained in uniquely assigned experimental rotational-vibrational transitions in order to obtain measured active rotational-vibrational energy levels (MARVEL). The procedure starts with collecting, critically evaluating, selecting, and compiling all available measured transitions, including assignments and uncertainties, into a single database. Then, spectroscopic networks (SN) are determined which contain all interconnecting rotational-vibrational energy levels supported by the grand database of the selected transitions. Adjustment of the uncertainties of the lines is performed next, with the help of a robust weighting strategy, until a self-consistent set of lines and uncertainties is achieved. Inversion of the transitions through a weighted least-squares-type procedure results in MARVEL energy levels and associated uncertainties. Local sensitivity coefficients could be computed for each energy level. The resulting set of MARVEL levels is called active as when new experimental measurements become available the same evaluation, adjustment, and inversion procedure should be repeated in order to obtain more dependable energy levels and uncertainties. MARVEL is tested on the example of the H₂¹⁷O isotopologue of water and a list of 2736 dependable energy levels, based on 8369 transitions, has been obtained.     

Emission features of Ho ion in Nb2O5, Ta2O5 and La2O3 mixed Li2O-ZrO2-SiO2 glasses

Li₂O-ZrO₂-SiO₂: Ho³⁺ glasses mixed with three interesting d-block elemental oxides, viz., Nb₂O₅, Ta₂O₅ and La₂O₃, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb₂O₅ and Ta₂O₅ mixed Li₂O-ZrO₂-SiO₂ glasses (free of Ho³⁺ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta⁵⁺ and Nb⁵⁺ ions in the glass network. The Judd-Ofelt theory was successfully applied to characterize Ho³⁺ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio β_r and the radiative lifetime τ_r, for ⁵S₂ emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for ⁵S₂ level of Ho³⁺ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La₂O₃ mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho³⁺ ions.     

CO2 laser assisted removal of UO2 and ThO2 particulates from metal surface

Pulsed laser assisted removal of uranium dioxide and thorium dioxide particulates from stainless steel surface have been studied using a TEA CO₂ laser. Decontamination efficiency is measured as a function of laser fluence and number of pulses. Threshold fluence for the removal of UO₂ particulates has been found to be lower than that required for the removal ThO₂ particulates. Usage of a ZnSe substrate, that is transparent to the laser wavelength used here, enabled us to decouple the cleaning effect arising out of absorption in the particulates from that in the substrate and has contributed towards understanding the mechanism responsible for cleaning. The experimental observations are also corroborated by simple theoretical calculations.     

An NMR study of the origin of dioxygen-induced spin-lattice relaxation enhancement and chemical shift perturbation

Due to its depth-dependent solubility, oxygen exerts paramagnetic effects which become progressively greater toward the hydrophobic interior of micelles, and lipid bilayer membranes. This paramagnetic gradient, which is manifested as contact shift perturbations (19F and 13C NMR) and spin-lattice relaxation enhancement (19F and 1H NMR), has been shown to be useful for precisely determining immersion depth, membrane protein secondary structure, and overall topology of membrane proteins. We have investigated the influence of oxygen on 19F and 13C NMR spectra and spin-lattice relaxation rates of a semiperfluorinated detergent, (8,8,8)-trifluoro (3,3,4,4,5,5,6,6,7,7)-difluoro octylmaltoside (TFOM) in a model membrane system, to determine the dominant paramagnetic spin-lattice relaxation and shift-perturbation mechanism. Based on the ratio of paramagnetic spin-lattice relaxation rates of 19F and directly bonded 13C nuclei, we conclude that the dominant relaxation mechanism must be dipolar. Furthermore, the temperature dependence of oxygen-induced chemical shift perturbations in 9F NMR spectra suggests a contact interaction is the dominant shift mechanism. The respective hyperfine coupling constants for 19F and 13C nuclei can then be estimated from the contact shifts <(deltav/v0)19F> and <(deltav/v0)13C>, allowing us to estimate the relative contribution of scalar and dipolar relaxation to 19F and 13C nuclei. We conclude that the contribution to spin-lattice relaxation from the oxygen induced paramagnetic scalar mechanism is negligible.     

Mechanism of relaxation enhancement of spin labels in membranes by paramagnetic ion salts: dependence on 3d and 4f ions and on the anions

Progressive saturation EPR measurements and EPR linewidth determinations have been performed on spin-labeled lipids in fluid phospholipid bilayer membranes to elucidate the mechanisms of relaxation enhancement by different paramagnetic ion salts. Such paramagnetic relaxation agents are widely used for structural EPR studies in biological systems, particularly with membranes. Metal ions of the 3d and 4f series were used as their chloride, sulfate, and perchlorate salts. For a given anion, the efficiency of relaxation enhancement is in the order Mn(2+) > or = Cu(2+) > Ni(2+) > Co(2+) approximately Dy(3+). A pronounced dependence of the paramagnetic relaxation enhancement on the anion is found in the order ClO(-)(4) > Cl(-) > SO(2-)(4). This is in the order of the octanol partition coefficients multiplied by spin exchange rate constants that were determined for the different paramagnetic salts in methanol. Detailed studies coupled with theoretical estimates reveal that, for the chlorides and perchlorates of Ni(2+) (and Co(2+)), the relaxation enhancements are dominated by Heisenberg spin exchange interactions with paramagnetic ions dissolved in fluid membranes. The dependence on membrane composition of the relaxation enhancement by intramembrane Heisenberg exchange indicates that the diffusion of the ions within the membrane takes place via water-filled defects. For the corresponding Cu(2+) salts, additional relaxation enhancements arise from dipolar interactions with ions within the membrane. For the case of Mn(2+) salts, static dipolar interactions with paramagnetic ions in the aqueous phase also make a further appreciable contribution to the spin-label relaxation enhancement. On this basis, different paramagnetic agents may be chosen to optimize sensitivity to different structurally correlated interactions. These results therefore will aid further spin-label EPR studies in structural biology.     

The VUV‐VIS Spectroscopic Properties of Dy3+ Ion in Phosphors M5‐2XDyXNaX(PO4)3F (M=Ca,Sr, Ba) and Their Potential Applications in Mercury‐Free Lamps

The phosphors, fluorapatites M₅(PO₄)₃F (M=Ca, Sr, Ba) activated with Dy³⁺ ions, were prepared by a high‐temperature solid‐state reaction technique. The VUV‐UV excitation spectra and emission spectra under VUV/UV excitation were measured. The phosphors show broad and strong absorption near 172 nm and intensive emission with the chromaticity coordinates entering the white light region. Hence, the phosphors may be considered as suitable candidates for Hg‐free lamps.