Spectrophotometric Study of Basicity of Some Substituted α-(Benzamtoomethyl)phenylhydrazines

The protonation behavior at 25°C in water and in aqueous sulfuric acid solutions of some substituted α-(p-R-benzamidomethyl)phenyl hydrazines (R=H, CH₃, Cl, Br) was investigated by UV spectrophotometry. The absorption spectra in sulfuric acid solutions were analyzed by the method of multivariate analysis. The premonition constants of hydrazine (pK₁) and amide (pK₂) moieties were determined; pK₂ values were calculated from the reconstituted absorption spectra by Cox - Yates method. Dependence of pK₂ on Hammett's a constants was discussed.     

The Mass Spectra of Substituted Diaryl α-Iminonitriles

The mass spectra of a series of substituted diaryl α-iminonitriles are reported. The most significant fragmentations arise from the following processes: (1) cleavage of the C-CN bond, (2) elimination of the R group from the substituted aryl ring, (3) formation of a phenyl cation (C₆H₅ ⁺), and (4) loss of a hydrogen atom from the parent ion. Anomolous behaviour was shown by the p-(t-butyl) derivative and reasons for this are discussed.     

Study of proton resonances in 18Ne via resonant elastic scattering of 17F + p and its astrophysical implication in the stellar reaction of 14O(α, p)17F

The stellar ¹⁴O (α, p) ¹⁷F reaction is thought to be one of the most important breakout reactions from the Hot CNO cycles into the rp-process in Type I X-ray bursters. In the present work, the properties of proton resonances in ¹⁸Ne have been investigated efficiently by utilizing a technique of proton resonant elastic scattering with a ¹⁷F radioactive-ion (RI) beam and a thick proton target. A 4.22 MeV/nucleon ¹⁷F RI beam, which was produced via a projectile-fragmentation reaction and experiencing a series of energy degradation, was separated by a Radioactive Ion Beam Line in Lanzhou (RIBLL) and bombarded a (CH₂)_n target. Energy spectra of the recoiled protons were measured by two sets of ΔE-E silicon telescope at center-of-mass scattering angles of θ _c.m. ≈ 175° ± 5°, θ _c.m. ≈ 152° ± 8°, respectively. Several proton resonances in ¹⁸Ne were observed, and their resonant parameters have been determined by an R-matrix analysis of the differential cross-sections. A doublet structure around 7.10 MeV has been identified and thought to be one state at 7.05 MeV (2⁺) and another one at 7.12 MeV (4⁺). The presently calculated total reaction rates of ¹⁴O (α, p) ¹⁷F are, at least, a factor of 1.2 ～ 1.9 larger than the previous ones in a temperature region of 1.7 ～ 3.0 GK mainly owing to the contribution from the 7.05 MeV (2⁺) state. This result implies that this breakout reaction may play a more important role than previously expected.     

NMR Studies of Drugs. Application of Achiral and Chiral Lanthanide Shift Reagents to α-Ethyl-α-Phenylsuccinimide

The 60 MHz ¹H NMR spectra of 3-ethyl-3-phenylpyrrolidine-2,5-dione, 1, were studied in CDCl₃ at 28° using 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, for spectral simplification, and the chiral LSR, tris[3-heptafluoropropylhydroxymethylene)-(+)-camphorato]-europium(III), Eu(HFC)₃ 3, to induce enantiomeric shift differences (δδδ) for several nuclei. A non-racemic sample of 1 was treated with 3 to determine the sense of magnetic nonequivalence of selected nuclei. Significant δδδ is seen for the signals of the methyl and aryl ortho protons. Modest δδδ can also be seen for the NH signal and for one of the H-4 protons, although LSR-induced broadening for the two latter signals is severe. The (-) enantiomer appeared to exhibit an upfield sense of magnetic nonequivalence (3:1 molar ratio ca. 0.15—0.35) for the methyl signal but a downfield sense for H_ortho (3:1 ratio ca. 0.6).     

Solid-state 17O NMR study of the electric-field-gradient and chemical shielding tensors in polycrystalline γ-glycine

We report the first experimental determination of the carboxylate oxygen electric-field-gradient (EFG) and chemical shielding (CS) tensors in polycrystalline γ-glycine. Analysis of magic-angle spinning (MAS) and stationary ¹⁷O NMR spectra of [¹⁷O]-γ-glycine obtained at 9.4, 14.1, 16.4, and 18.8 T yields the magnitudes of the ¹⁷O EFG and CS tensors and the relative orientations between the two tensors. Extensive quantum chemical calculations at both the restricted Hartree–Fock and density functional levels have been performed to present the absolute tensor orientations in term of the molecular frame. We have demonstrated that ¹⁷O NMR tensor information could be unambiguously derived by the multiple field analyses of stationary ¹⁷O NMR spectra.     

Study of the Defect Structure and Crystal-Field Parameters of α-Al2O3:Yb3+

The methods currently used for studying the defect structure of laser host crystals doped with transition metal or rare-earth ions have several drawbacks or limitations. This study proposes an alternative approach for obtaining optimized impurity structures using molecular dynamics calculation in conjunction with the superposition model. This new approach is specifically applied to a system named α-Al₂O₃:Yb³⁺, in which the simulated defect structure is used to fit the superposition model parameters directly onto the observed energy levels. Such an approach provides predicted values of crystal-field parameters, Zeeman splitting g-factor, and hyperfine structure constants. Moreover, the C_3v site symmetry is found to be a good approximation for the actual C₃ site of Yb³⁺, as doped in an α-Al₂O₃ crystal.     

羧酸中羟基17O NMR化学位移计算方法的改进

讨论羧酸类化合物中羟基¹⁷O NMR 化学位移计算方法的改进. 该化合物包括饱和脂肪酸、不饱和脂肪酸、苯甲酸、苯乙酸、苯丙烯酸和氨基酸等. 提出Δα的新计算参数.     

Mechanochemical Transformations in α-Fe2O3 – ICEMS Study

Integral conversion electron Mössbauer spectroscopy has been used to investigate the phases and transformations which occur when -Fe₂O₃ is wet-milled in vacuum for up to 144 h. In addition to the transformation to off-stoichiometric Fe_3–x O₄ observed previously by transmission Mössbauer spectroscopy, the room temperature ICEMS spectra reveal the presence of 10–15% -Fe₂O₃ on the surfaces of particles milled for more than 24 h. Time-of-flight neutron diffraction of an -Fe₂O₃ sample wet-milled for 200 h also provides evidence of the occurrence of a small fraction (4%) of -Fe₂O₃ in the milled product. The -Fe₂O₃ is likely to occur as a surface oxide layer and does not appear to play a significant role in the mechanochemical transformation of -Fe₂O₃ to Fe_3–x O₄.     

Study on the orthonormalization eigenstates of α_q~3

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A Study of Intermediate Energy Proton-^16O Elastic Scattering Based on the α-Particle Model

In the framework of KMT multiple scattering theory, an optical potential for the intermediate energy proton-160 elastic scattering is presented based on the α particle model of 160. The differential cross sections, the analyzing powers, and the total cross sections of the intermediate energy proton-160 scattering have been calculated by using the obtained optical potential. The main features of the measured angular distributions of the cross section and the analyzing power can be well described. The calculated total cross sections are in good agreement with the experimental data at energies below 0.7 GeV and underestimate the data about 8% at higher energies.     

In situ 1H NMR Study of Nanoreactor Interaction NH3–H2O in Zeolite Nanopores

The interaction between ammonium NH₃ and H₂O molecules in zeolitic nanopores is studied by in situ ¹H nuclear magnetic resonance (NMR) method. The powder and single crystal samples of natural zeolites, heulandites Ca₄[Al₈Si₂₈O₇₂]·24H₂O and clinoptilolite (Na, K,Ca_1/2)₆[Al₆Si₃₀O₇₂], were used as the model system. It is shown that penetration of NH₃ into the zeolitic nanopores is accompanied by disordering of the hydrogen sublattice of zeolitic water and by the fast proton exchange NH₃ + H₂O ? [NH₄]⁺ + [OH]^? characterized by correlation frequency v _c = ~40 kHz. Another nanoreactor interactions are represented by interaction of [NH₄]⁺ ions with exchangeable Na⁺ and Ca²⁺ ions of the zeolitic structure. The slow ionic exchange [NH₄]⁺ → [Na,Ca_1/2]⁺ and binding of [NH₄]⁺ in cationic sites of the framework were visualized by NMR spectroscopy along with stepwise release of (Na,Ca_1/2)OH from zeolitic pores to the external surface of zeolite grains.     

α-Decay half-lives, α-capture cross sections, and α-nucleous interaction

The expression for the α-nuclear potential was found. This potential describes the α-decay half-lives for the ground states of nuclei and the α-particle capture cross sections for ⁴⁰Ca, ⁴⁴Ca, ⁵⁹Co, ²⁰⁸Pb, and ²⁰⁹Bi nuclei well. The potential was used to calculate the probabilities of α-transitions from the ground states of parent nuclei to different excited states of daughter nuclei. Simple analytical relations for calculating α-decay half-lives for transitions between the ground states of nuclei are determined.     

Study of low temperature ferromagnetism,surface paramagnetism and exchange bias effect in α-Fe1.4Ga0.6O3 oxide

The compound α-Fe_1.4Ga_0.6O₃ has been prepared by mechanical alloying of α-Fe₂O₃ and β-Ga₂O₃ and subsequent heating under vacuum condition. X-ray diffraction, Raman and Mössbauer spectroscopy confirmed stabilization of the material in rhombohedral phase. A remarkable change in the magnetic ordering has been found by substitution of non-magnetic Ga atoms in α-Fe₂O₃. The ferromagnetism in α-Fe_1.4Ga_0.6O₃ is found to be more soft and enhanced in comparison to α-Fe₂O₃. The samples also exhibited features of exchange bias, low temperature surface paramagnetism, and suppression of Morin transition. Nano-sized grains and alloying process of the material affected these features up to certain extent. The results of magnetic measurements are highly interesting for designing metal doped α-Fe₂O₃ based ferromagnet for room temperature applications.     

NMR spectra of 3β-hydroxy-5α-cholane derivatives,zymosterol synthesis intermediates

Proton and carbon resonances in NMR spectra of a number of derivatives of 3β-hydroxy-5α-cholanes, zymosterol synthesis intermediates, have been completely assigned using 2D NMR spectroscopy methods. The stereochemistry of the chiral centers and the structures of the molecules have been confirmed.     

Determination of the Structure and Configuration of 16α-Fluoro-5-androsten-17-one by NMR Spectroscopy and X-ray Diffraction

The stereochemistry of 16α-fluoro-5-androsten-17-one (1) was determined by nmr spectroscopy and X-ray diffraction. The γ-effects of the fluorine atom in ¹³C nmr were used as a first stereochemical probe for the α-fluorine configuration. The magnitude of ³J (HH) measured on the H-16 multiplet of the 300 MHz ¹H nmr spectrum of compound 1, was used with Karplus-type plots for the CH₂CHF fragment of the two possible epimers. The plots show that only the α-fluorine configuration fits with the observed ³J (HH), and X-ray diffraction confirms such result. The dihedral angles estimated from the Karplus-type plot were consistent with the angles found by X-ray. Crystallographic data of compound 1 show the following ring conformations: A is a chair, B is an 8β, 9α-half-chair, C is a chair and D is a C(13)β-envelope.     

A Study of Antiferromagnetic Ordering in β-FeF3·3H2O by the Use of the NMR Method

The present work cites the investigation results of local magnetic fields on ¹H and ¹⁹F nuclei and spin ordering in β-FeF₃·3H₂O. In the structure of this compound (space group P4₂/n, a=7.846 Å, c=7.754 Å, z=4^1,2) Fe atoms are bonded via bridged F atoms (1) in infinite chains along the /001/ axis. With such positioning, in which two paramagnetic atoms are separated by a diamagnetic atom (F, O, C1 and others) there is a possibility for indirect (superexchange) interaction. Linear chains … Fe - F - Fe - F - Fe - F … are separated from each other by F(2) atoms and water molecules H₂O (1) and H₂O (2), so that exchange between neighboring Fe atoms from various chains is ostensibly much encumbered.     

Spectroscopic techniques (Mössbauer spectrometry,NMR, ESR,…) as tools to resolve doubtful NMR images: Study of the craniopharyngioma tumor

Craniopharyngioma, an intracranial tumor, exhibits hyperintensity in the Spin-Echo-T₂-NMR image and a hyposignal in the SE-T₁-image. However, in some cases (15–20% cases), hypersignals are seen in both SE-T₁ and T₂-MRI. Using spectroscopic techniques, Mössbauer spectrometry in particular, we have demonstrated that the T₁ hypersignal is due to ferritin, dissolved in the cystic liquid, after tumor cell lysis, in the course of time. Other possible reasons inducing a shortening of the T₁ relaxation time (presence of lipids, intratumoral hemorrhage) have been rejected.     

Search for the 70 keV resonance in17O(p, α)14N

A direct search for theE _R =70 keV resonance in¹⁷O(p, )¹⁴N was carried out using¹⁷O enriched Ta₂O₅ targets in combination with a 1 mA proton beam and suitable detectors of large solid angle. The observed upper limit for the resonance strength is8×10^–10 eV.Work supported in part by Deutsche Forschungsgemeinschaft (Ro429/21-2) and the Science Program SC1-0065 of the European Economic Community