Effect of Shift Reagents on Infrared Spectra

Abstract

Introduction

We have shown previously¹ that when Eu(fod)₃?d₂₇ shift reagent is added to the erythro and threo esters of 2,3-diphenyl-3-hydroxypropanoic acid, the vicinal coupling constants, J₂₃, vary in a manner which indicates bidentate coordination.     

Laser-radiofrequency double-resonance spectroscopy of 13CH3I

Pure quadrupole resonances of the I¹²⁷ nucleus of ¹³CH₃I have been observed using laser-radiofrequency double resonance. Quadrupole coupling constants are reported for the ground, ν₃, 2ν₃, ν₆, 2ν₆, ν₃ + ν₆, and 2ν₃ + 2ν₆ states. Smaller hyperfine constants are also reported for the ground and ν₆ states.     

Influence of pressure on the relative population of the two lowest vibrational levels of the C <Superscript>3</Superscript> Π<Subscript>u</Subscript> state of nitrogen for electron beam excitation

Continuous and pulsed 12 keV electron beams were used to excite nitrogen within a gas cell at pressures ranging from 10 to 1400 hPa. The pressure dependence of the ratio of photon fluxes for emission from vibrational levels v'=0 and 1 of the C ³Π _u state has been studied. The results confirm the presence of a collisional excitation mechanism populating v'=0, 1 in addition to electron impact excitation. Rate constants of (1.27 ±0.04)×10^-11 cm³s^-1 [ v'=0] and (2.68 ±0.08)×10^-11 cm³s^-1 [ v'=1] were measured for C ³Π _u quenching by ground state nitrogen. For electron beam conditions relative excitation efficiencies of 1:0.59:0.22 for vibrational levels 0, 1 and 2 were calculated. The recorded flux ratios are compared with the predictions given by a vibrational relaxation model.     

N+BF<Subscript>2</Subscript> and N+C+BF<Subscript>2</Subscript> high-dose co-implantation in silicon

Nitrogen and boron BF₂, and nitrogen, carbon, and boron BF₂ high-dose (6×10¹⁶–3×10¹⁷ cm^-2) co-implantation were performed at energies of about 21–77 keV. Subsequent high-temperature annealing processes (600, 850, and 1200 °C) lead to the formation of three and two surface layers respectively. The outer layer mainly consists of polycrystalline silicon and some amorphous material and Si₃N₄ inclusions. The inner layer is highly defective crystalline silicon, with some inclusions of Si₃N₄ too. In the N+B-implanted sample the intermediate layer is amorphous. Co-implantation of boron with nitrogen and with nitrogen and carbon prevents the excessive diffusivity of B and leads to a lattice-parameter reduction of 0.7–1.0%. Received: 10 January 2002 / Accepted: 30 May 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +34-91/3974895; E-mail: Lucia.Barbadillo@uam.es     

Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS

Cr/SiO₂ catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr⁶⁺ and Cr³⁺ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr⁶⁺ to Cr³⁺ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO₃ and Cr₂O₃ standards did not reveal variation in the binding energy of Cr 2p_3/2, but a physical mixture of CrO₃ with SiO₂ presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed.     

Lanthanide Shift Reagents XIV Equilibrium Binding Constants for Europium Shift Reagent with Alkyl and Aryl Esters

Methods have been developed for measuring the equilibrium binding constants (K) for lanthanide shift reagents with donor substrates. Although Infrared Spectroscopy proved useful¹ for determining the binding of substituted anilines to the tris-tetramethylheptanedionate of Ytterbium, it was found that NMR was more sensitive and applicable to a wider range of substrates than simple alcohols and amines^2,3. The NMR procedure of progressive     

NMR Studies of Drugs: Antipyrine and Analogs. I. Use of Achiral and Chiral Lanthanide Shift Reagents to Examine Hindered Rotation.

The 200 MHz ¹H NMR spectra of the analgesic, antipyrine, 1, have been studied in CDC1₃ solution at ambient temperatures with the achiral lanthanide shift reagent (LSR) tris (6, 6, 7, 7, 8, 8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) europium (III), Eu(FOD)₃, 2, and with the chiral LSR, tris[3-(heptafluoropropylhydroxymethylene)-(+)-camphorato]europium(III), Eu(HFC)₃, 3., Lanthanide-induced shift (LIS) magnitudes and broadening of selected signals are consistent with predominant LSR binding at the carbonyl oxygen with either 2 or 3. Of the different possible conformational regimes for the N-phenyl group of 1, our results appear to rule out a slow exchange limit (SEL) system with the N-phenyl coplanar with the heterocyclic ring. Perpendicular rings in an SEL regime can not be ruled out. A rapidly-rotating N-phenyl (fast exchange limit, FEL system) would also be consistent with observed results. Accurate chemical shifts for the aryl protons (overlapped in the 200 MHz spectrum of unshifted 1) are determined from spectra with added LSR by extrapolation to zero molar ratios of [LSR]:[1]. Relative slopes in the plots of chemical shift versus [LSR]:[1] molar ratios are calculated for each proton signal of 1.     

Crystalline structure and optical spectroscopy of Er3+-doped KGd(WO4)2 single crystals

4 )₂ single crystals doped with Er³⁺ have been grown by the flux top-seeded-solution growth method. The crystallographic structure of the lattice has been refined, being the lattice constants a=10.652(4), b=10.374(6), c=7.582(2) Å, β=130.80(2)°. The refractive index dispersion of the host has been measured in the 350–1500 nm range. The optical absorption and photoluminescence properties of Er³⁺ have been characterised in the 5–300 K temperature range. At 5 K, the absorption and emission bands show the (2J+1)/2 multiplet splittings expected for the C₂ symmetry site of Er in the Gd site. The energy positions and halfwidths of the 72 sublevels observed have been tabulated as well as the cross sections of the different multiplets. Six emission band sets have been observed under excitation of the ⁴F_7/2 multiplet. The Judd–Ofelt (JO) parameters of Er³⁺ in KGW have been calculated: Ω₂=8.90×10^-20 cm², Ω₄=0.96×10^-20 cm², Ω₆=0.82×10^-20 cm². Lifetimes of the ⁴S_3/2, ⁴F_9/2, and ⁴I_11/2 multiplets have been measured in the 5–300 K range of temperature and compared with those calculated from the JO theory. A reduction of the ⁴S_3/2 and ⁴I_11/2 measured lifetimes with increasing erbium concentration has been observed, moreover the presence of multiphonon non-radiative processes is inferred from the temperature dependence of the lifetimes. Received: 15 December 1997/Revised version: 10 July 1998     

NMR Studies of Drugs. 5-Methyl-5-phenylhydantoin. Applications of Lanthanide Shift Reagents in Polar Solvents to a Non-Chelating Substrate

The 200.1 MHz ¹H NMR spectra of 5-methyl-5-phenylhydantoin, 1, have been studied in CD₃CN solution at ambient temperatures with the achiral shift reagent, tris (6, 6, 7, 7, 8, 8, 8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium (III), 2, and the chiral reagent, tris[3-(heptafluoropropylhydroxymethylene)-(+)-camphorato] europium (III), 3. Although 1 cannot chelate the LSRs, use of sufficiently high LSR:1 molar ratios served to compensate for competitive binding of LSR by the polar solvent, and permitted substantial lanthanide-induced shifts to be observed with 2 or 3. With 3, significant enantiomeric shift differences were produced for the ortho aryl protons and for the CH₃ signals. The ortho proton signal appears to offer excellent potential for direct determination of enantiomeric excess of 1. These results demonstrate the utility of LSRs 2 or 3 even in a polar solvent with a nonchelating substrate.     

Enhancement of minority carrier lifetime in GaAs1? x P x ( x =0.4; 0.65) by nitrogen implantation

Minority carrier lifetimes in nitrogen implanted GaAs_1-x P _x (x=0.4; 0.65) were measured at 77K by an optical phase shift method as a function of nitrogen dose and annealing temperature in order to investigate the dependence of the lifetime on the concentration of nitrogen isoelectronic traps. A large increase in the lifetime was observed after nitrogen implantation followed by annealing at and above 800°C. The maximum lifetimes were 22ns for GaAs_0.35P_0.65 and 6.7 ns for GaAs_0.6P_0.4. They were obtained by implantation to a dose of 5×10¹³ cm⁻² in GaAs_0.35P_0.65 and 10¹³ cm⁻² in GaAs_0.6P_0.4. The lifetime after nitrogen implantation followed by annealing was longer by a factor of 6–7 than that of the unimplanted sample.     

Force Constants,Coriolis Coupling Constants,and Mean Amplitudes of Vibration of InCl6 3-

Abstract

The general quadratic force constants, coriolis coupling constants and mean amplitudes of vibration have been evaluated for InCl₆ ^3- using recent vibrational data. The results are employed to study the trend of variation in the isoelectronic sequences e.g. InCl₆ ^3-, SnCl₆ ^2- and SbCl₆ ^?.

In the present communication we report the force constants, coriolis coupling constants and mean amplitudes of vibration for InCl₆ ^3- which have not been reported so far. The results are used to study the trend of variation of the molecular parameters in the isoelectronic sequence e.g. InCl₆ ^3-, SnCl₆ ^2- and SbCl₆ ^?. The fundamental frequencies of InCl₆ ^3-, employed in this computation, have been reported on the basis of octahedral symmetry, from infrared and Raman Spectral Studies¹.     

The Muonic Hydrogen Lamb Shift Experiment at PSI

A measurement of the 2S Lamb shift in muonic hydrogen (μ⁻p) is being prepared at the Paul Scherrer Institute (PSI). The goal of the experiment is to measure the energy difference ΔE(2⁵ P _3/2−2³ S _1/2) by laser spectroscopy (λ≈6μm) to a precision of 30 ppm and to deduce the root mean square (rms) proton charge radius with 10⁻³ relative accuracy, 20 times more precise than presently known. An important prerequisite to this experiment is the availability of long-lived μp_2S -atoms. A 2S-lifetime of ∼1 μs – sufficiently long to perform the laser experiment – at H₂ gas pressures of 1–2 hPa was deduced from recent measurements of the collisional 2S-quenching rate. A new low-energy negative muon beam yields an order of magnitude more muon stops in a small low-density gas volume than a conventional cloud muon beam. A stack of ultra-thin carbon foils is the key element of a fast detector for keV-muons. The development of a 2 keV X-ray detector and a 3-stage laser system providing 0.5 mJ laser pulses at 6 μm is on the way. This revised version was published online in August 2006 with corrections to the Cover Date.     

CHCl3电子吸附速率常数的离子迁移谱

利用电晕放电离子迁移谱, 使用高纯氮气作为载气和迁移气体, 研究了电场强度在200～500 V/cm变化时CHCl₃的解离电子吸附速率常数, 得到样品所对应的电子吸附速率常数为1.26×10^-8～8.24×10^-9 cm³/(molecules s)．利用该装置测量了固定电场下,样品的电子吸附速率常数与样品浓度之间的关系．此外利用所获得的离子迁移谱图得到了不同电场强度下Cl^-与CHCl₃之间的离子分子反应速率常数.     

NMR Studies of Agricultural Products. Applications of Achiral and Chiral Lanthanide Shift Reagents to the Fungicide,Triadimefon.

Abstract

The 60 MHz ¹H NMR spectra of the systemic agricultural fungicide, triadimefon, 1, have been studied in CDCl₃ at 28±1° (as the racemic free base) with the added achiral lanthanide shift reagent (LSR), tris(6, 6, 7, 7, 8, 8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) europium(III), Eu(FOD)₃, 2, for spectral simplification, and with the chiral LSR, tris [3-(heptafluoropropylhydroxymethylene)-(+) -camphorato)europium(III), Eu(HFC)₃, 3, to induce enantiomeric shift differences (ΔΔδ) for several nuclei. Significant ΔΔδ values were seen for the two protons of the heterocyclic ring, the OCH methine, and aryl H-2′, 6′ of the chlorophenoxy ring. For each of these nuclei exhibiting ΔΔδ with added 3, the ΔΔδ magnitudes reached maximum values with 3: 1 molar ratios ca. 0. 18–0. 29, and decreased with higher levels of 3. To confirm analytical utility of 3 for % e. e. determinations of 1, a nonracemic (“spiked”) sample of racemic 1, with added R-(?) triadimefon, was examined with 3. At low 3: 1 ratios, both triazole H-3 and H-5, as well as the OCH and aryl H-2′, 6′ protons of (?)-1 showed a downfield sense of magnetic nonequivalence with (+) -3. With 3: 1 ratios ca. 0. 8, triazole proton H-3 reversed its sense of magnetic noneguivalence. The H-3 and H-5 signals were useful for % e. e determinations at this higher 3: 1 ratio.     

NMR Studies of Drugs. Applications of Achiral and Chiral Wthanide Shift Reagents to Bupropion

Abstract

The ¹H NMR spectra of racemic samples of the antidepressant drug, bupropion, 1, have been studied in CDCl₃ solution at 60 and 200 MHz with the achiral lanthanide shift reagent (LSR), tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium (III), 2, and the chiral reagent, tris[3-(heptafluoropropylhydroxymethylene)-d-camphorato]europium(III), 3. Both LSR produced substantial lanthanide induced shifts consistent with ¹H assignments, but the bound complexes of 1 with 2 versus 3 may not be isostructural. With 3, substantial enantiomeric shift differences were observed for the t-butyl, CH ₃CH, NCH, and the aryl H-2 and H-6 signals, which should permit potential direct determination of enantiomeric excess.     

Microwave spectra and structure of an isoxazole-water complex

The rotational spectrum of a hydrogen-bonded isoxazole-water complex has been measured between 6–18 GHz with a pulsed nozzle Fourier transform microwave spectrometer. In addition to isoxazole-H₂O, the complexes with HDO and D₂O as well as isoxazole-¹⁵ N-H₂O have been investigated in order to determine the structure of the complex. Rotational constants, quartic centrifugal distortion constants and quadrupole coupling constants, where applicable, have been fitted to the measured transition frequencies of the isotopomers. Structural data, which have been deduced from the planar moments of inertia and the quadrupole coupling constants of the isotopomers, have established conclusively that water binds to nitrogen in the ring plane of isoxazole. Ab initio calculations have revealed that complexes with a hydrogen-bond to nitrogen or to oxygen are both stable. The complex with water attached to nitrogen has been found to be more strongly bound than that with water attached to oxygen. Small splittings of the rotational transitions of the two complexes with H₂O have been interpreted as being the result of an internal rotation of water with respect to isoxazole.     

LSP spectral changes correlating with SERS activation and quenching for R6G on immobilized Ag nanoparticles

In terms of chemical enhancement in Surface Enhanced Raman Scattering (SERS), we investigated the effect of halide and other anions to rhodamine 6G (R6G) adsorbed Ag particles that were immobilized on the substrates. The residual species on chemically prepared Ag particles such as citrate or a-carbon were thoroughly substituted by various anions, e.g., Cl⁻, Br⁻, I⁻, SCN⁻, CN⁻, or S₂O₃ ²⁻ anions, whose adsorption features are elucidated by the formation constants for AgX₂ ^(m−1)−, here X denotes the above anions. In particular, Cl⁻, Br⁻, or SCN⁻ ions activated SERS of R6G via intrinsic electronic interaction with Ag, whereas CN⁻, S₂O₃ ²⁻, or I⁻ anions quenched it due to their exclusive adsorption onto the Ag surfaces. We found that the activation process with the anions commonly yields a marked blue-shift of the coupled plasmon peak from ca. 650–700 to 500–550 nm in elastic scattering. It is rationalized by slight increase of the gap size between adjacent Ag nanoparticles by only ca. 1 nm based on theoretical simulations. This is probably caused by slight dissolution, oxidative etching, of the particles according to large formation constants of the complexes. Consequently, partly remaining negative charges on the Ag surface, and a slight increase in the gap size, providing huge electric field, facilitated R6G cations to adsorb on the nanoparticles, especially at the junction.     

NMR Studies of Drugs. Applications of Lanthanide Shift Reagents to Afloqualone,an Axially Chiral Quinazolinone.

The skeletal muscle relaxant, aflogualone, 1, has been studied by ¹H NMR in CDC1₃ at 60 and 300 MHz in the presence of added chiral [Eu(HFC)₃] or achiral [Eu(FOD)₃] lanthanide shift reagents (LSR). With Eu(HFC)₃, significant enantiomeric shift differences, ΔΔδ, can be induced for most of the nuclei of 1, with near-baseline resolution obtainable for the H-5 signals of each enantiomer, indicating excellent analytical potential for direct determination of enantiomeric excess of samples of 1. Observation of ΔΔδ directly confirms hindered rotation about the bond between N (3) and the 2-methylphenyl group, i.e., the N (sp²) - C(sp²) bond, leading to axial chirality in 1 with slow rotation on the NMR timescale. Assignments are supported by 2D COSY spectra at 300 MHz. Relative lanthanide-induced shift magnitudes for the protons of 1 are compared.     

NMR Studies of Drugs. 1H and 13C NMR Chemical Shift Assignments in Etidocaine and Etidocaine Hydrochloride Determined by Two-Dimensional NMR Spectroscopy

¹H and ¹³C NMR chemical shift assignments were obtained for the local anesthetics etidocaine (1) and etidocaine hydrochloride (2) in CDCl₃ solution, as well as for 2 in D₂O solution. The COSY experiment was employed for proton-proton correlation, while onebond and long-range 2D heteronuclear techniques allowed the assignments of all ¹³C chemical shifts in each molecule. Etidocaine has a chiral carbon; etidocaine hydrochloride has, in addition to the natural chiral center, an acid-induced chirality at the protonated amine nitrogen, resulting in solvent-dependent diastereomers. Ten of the fourteen magnetically nonequivalent ¹³C nuclei of 2 exhibit doubled ¹³C resonance peaks (50.3 MHz, 20°C, CDCl₃ solution) due to the presence of the two diastereomers.     

Spin-Labelling of RUBP Carboxylase-Oxygenase from Puma Rye. I. Properties of the Labelled Enzyme

Abstract

This report describes the first application of nitroxide spin labels to the study of structure and function relationships in RUBP carboxylase. RUBPCase (EC 4.1.1.39) is known to be allosterically regulated by several metabolites. Lorimerc et al. (1) characterized the activation kinetics of RUBPCase by CO₂ and Mg²⁺ and its inhibition by RUBP. Chu and Bassham (2, 3, 4) showed that effectors such as NADPH and PGA stimulated the enzyme only when present in the preincubation medium containing HCO^? ₃ and Mg²⁺. Buchanan and Schurmann (5) and Vater and Salinkow (6) reported activation of carboxylase activity by fructose-6-phosphate and 6-phosphoglucon teal.

Evidence for structural changes in RUBPCase upon binding of ligands has been reported. Kwok and Wildman (7) provided evidence of a conformational change in tobacco RUBPCase induced by the binding of RUBP which was recently supported by Grebanier et al. (8).