高效液相色谱法测定依托咪酯异构体杂质

建立了依托咪酯异构体杂质的高效液相色谱（HPLC）方法,采用AD-H柱,流速0.8 mL/min,检测波长235 nm.经方法学验证,该方法对依托咪酯及其异构体专属性确认分离度大于2.0,对依托咪酯异构体杂质的最小检测限（LOD）为0.002％,线性范围为0.001 6.μg～0.052 6 μg,相关系数r=0.999 44,加样回收率分别为82.0％、90.5％和96.2％.结果表明该检测方法专属性好,灵敏度高,准确,用于依托咪酯异构体杂质测定结果可靠.     

Differentiation of isomeric dinitrotoluenes and aminodinitrotoluenes using electrospray high resolution mass spectrometry

Explosive detection and identification play an important role in the environmental and forensic sciences. However, accurate identification of isomeric compounds remains a challenging task for current analytical methods. The combination of electrospray multistage mass spectrometry (ESI‐MSⁿ) and high resolution mass spectrometry (HRMS) is a powerful tool for the structure characterization of isomeric compounds. We show herein that resonant ion activation performed in a linear quadrupole ion trap allows the differentiation of dinitrotoluene isomers as well as aminodinitrotoluene isomers. The explosive‐related compounds: 2,4‐dinitrotoluene (2,4‐DNT), 2,6‐dinitrotoluene (2,6‐DNT), 2‐amino‐4,6‐dinitrotoluene (2A‐4,6‐DNT) and 4‐amino‐2,6‐dinitrotoluene (4A‐2,6‐DNT) were analyzed by ESI‐MS in the negative ion mode; they produced mainly deprotonated molecules [M ? H]^?. Subsequent low resolution MSⁿ experiments provided support for fragment ion assignments and determination of consecutive dissociation pathways. Resonant activation of deprotonated dinitrotoluene isomers gave different fragment ions according to the position of the nitro and amino groups on the toluene backbone. Fragment ion identification was bolstered by accurate mass measurements performed using Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR/MS). Notably, unexpected results were found from accurate mass measurements performed at high resolution for 2,6‐DNT where a 30‐Da loss was observed that corresponds to CH₂O departure instead of the expected isobaric NO^? loss. Moreover, 2,4‐DNT showed a diagnostic fragment ion at m/z 116, allowing the unambiguous distinction between 2,4‐ and 2,6‐DNT isomers. Here, CH₂O loss is hindered by the presence of an amino group in both 2A‐4,6‐DNT and 4A‐2,6‐DNT isomers, but nevertheless, these isomers showed significant differences in their fragmentation sequences, thus allowing their differentiation. DFT calculations were also performed to support experimental observations. Copyright © 2014 John Wiley & Sons, Ltd.     

Measurements of natCd(γ, x) reaction cross sections and isomer ratio of 115m,gCd with the bremsstrahlung end-point energies of 50 and 60 MeV

The flux-weighted average cross sections of ^natCd(γ, xn)^{115g,m,111m,109,107,105,104}Cd and ^natCd(γ, x)^{113g,112,111g,110m}Ag reactions were measured at the bremsstrahlung end-point energies of 50 and 60 MeV. The activation and off-line γ-ray spectrometric technique was carried out using the 100 MeV electron linear accelerator at the Pohang Accelerator Laboratory, Korea. The ^natCd(γ, xn) reaction cross sections as a function of photon energy were theoretically calculated using the TALYS-1.95 and the EMPIRE-3.2 Malta codes. Then, the flux-weighted average cross sections were obtained from the theoretical values of mono-energetic photons. These values were compared with the flux-weighted values from the present study and were found to be in general agreement. The measured experimental reaction cross-sections and integral yields were described for cadmium and silver isotopes in the ^natCd(γ, xn)^{115g,m,111m,109,107,105,104}Cd and ^natCd(γ, x)^{113g,112,111g,110m}Ag reactions. The isomeric yield ratio (IR) of ^115g,mCd in the ^natCd(γ, xn) reaction was determined for the two bremsstrahlung end-point energies. The measured isomeric yield ratios of ^115g,mCd in the ^natCd(γ, xn) reaction were also compared with the theoretical values of the nuclear model codes and previously published literature data of the ¹¹⁶Cd(γ, n) and ¹¹⁶Cd(n, 2n) reactions. It was found that the IR value increases with increasing projectile energy, which demonstrates the characteristic of excitation energy. However, the higher IR value of ^115g,mCd in the ¹¹⁶Cd(n, 2n) reaction compared to that in the ¹¹⁶Cd(γ, n) reaction indicates the role of compound nuclear spin alongside excitation energy.     

Combining UV photodissociation with electron transfer for peptide structure analysis

The combination of near‐UV photodissociation with electron transfer and collisional activation provides a new tool for structure investigation of isolated peptide ions and reactive intermediates. Two new types of pulse experiments are reported. In the first one called UV/Vis photodissociation–electron transfer dissociation (UVPD‐ETD), diazirine‐labeled peptide ions are shown to undergo photodissociation in the gas phase to form new covalent bonds, guided by the ion conformation, and the products are analyzed by electron transfer dissociation. In the second experiment, called ETD‐UVPD wherein synthetic labels are not necessary, electron transfer forms new cation–peptide radical chromophores that absorb at 355 nm and undergo specific backbone photodissociation reactions. The new method is applied to distinguish isomeric ions produced by ETD of arginine containing peptides. Copyright © 2015 John Wiley & Sons, Ltd.     

Theoretical investigation on structures,stability and properties of [P,X, Y] (X=C,Si; Y = O,S) isomers

The structures, energetics and stability of the [P, X, Y] (X?=?C, Si; Y?=?O, S) radicals are explored by means of the density functional theory and ab initio levels. Seventeen [P, X, Y] isomers and 14 interconversion transition states are obtained at the B3LYP/6-311G(d) level. At the CCSD(T)/6-311?+?G(2df)//QCISD/6-311G(d)?+?ZPVE level, the lowest-lying isomers are the linear PCO 1a (0.0?kcal/mol), PCS 1b (0.0) and the three-membered ring cPSiO 1c (0.0), cPSiS 1d (0.0) on their respective potential energy surfaces. These four isomers exhibit considerably not only thermodynamic but also kinetic stabilities. Additionally, the cyclic cPCS 2b (32.8) and linear PSiS 2d (18.6) possess also high kinetic stability. All of six isomers 1a, 1b, 2b, 1c, 1d and 2d are considerably stabilized by a barrier of at least 20?kcal/mol, and may be detected in the laboratory or interstellar space. Their valence bond structures and possible formation strategies in the laboratory and space are discussed in detail. Finally, the similarities and discrepancies on structures and stabilities between [P, X, Y] (X?=?C, Si; Y?=?O, S) isomers are compared. These predicted results are highly expected to be informative for the future identification of [P, X, Y] (X?=?C, Si; Y?=?O, S) in the laboratory and space.     

Mössbauer effect studied in rare-earth oxides (REu)O3 (R = Pr,Nd, Sm)

Abstract

Both X-ray diffraction and the Mössbauer effect have been used to study the double rare-earth oxide solid solutions (REu)O³ (R = Pr, Nd, Sm), which were synthesized with a combination of high pressure and high temperature for the first time. It is shown that all products are of the B-type (monoclinic) structures of single phase. The hyperfine interactions depend strongly on the ligand volume of Eu ions.     

Cationic ring‐opening polymerization behavior of a five‐membered cyclic thiocarbonate having a spiro‐linked adamantane moiety

This work deals with the synthesis and cationic ring‐opening polymerization behavior of a novel five‐membered cyclic thiocarbonate bearing a spiro‐linked adamantane moiety, tricyclo[3.3.1.1^3,7]decane‐2‐spiro‐4′‐(1′,3′‐dioxolane‐2′‐thione) ( TC2 ). The cationic ring‐opening polymerization of TC2 did not proceed with trifluoromethanesulfonic acid, methyl trifluoromethanesulfonate, triethyloxonium tetrafluoroborate (Et₃OBF₄), boron trifluoride etherate (BF₃OEt₂), titanium tetrachloride, or methyl iodide as the initiator, presumably because of the steric hindrance of the adamantane moiety. However, the cationic ring‐opening copolymerization of TC2 with five‐ or six‐membered cyclic thiocarbonates, that is, 1,3‐dioxolane‐2‐thione, 1,3‐dioxane‐2‐thione, 5‐methyl‐1,3‐dioxane‐2‐thione, or 5,5‐dimethyl‐1,3‐dioxane‐2‐thione, initiated by BF₃OEt₂ or Et₃OBF₄, proceeded to afford the corresponding copolymer via a selective ring‐opening direction. The increase in the feed ratio of TC2 in the copolymerization increased the unit ratio derived from TC2 in the copolymer; however, the molecular weight of the copolymer decreased. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 699–707, 2003     

Simultaneous determination of nitrophenol isomers at the single-wall carbon nanotube compound conducting polymer film modified electrode

One of the challenging areas of electrochemistry and electroanalytical chemistry is the simultaneous determination of isomers at the same electrode. Con- ventional electrode only possesses a single function of electron transfer; therefore, it is difficult…     

High-spin states of 125Sb: Particle-core excitation coupling

Excited states of 125Sb have been studied using in-beam γspectroscopy techniques via the 124Sn(7Li, α2n) reaction at a beam energy of 32 MeV. A high-spin level scheme including 21 new γ-transitions and 14 new excited states have been established. Three isomers have been identified at 1970, 2110 and 2471 keV and the ranges of their half-lives have been estimated from the delayed coincidence data. The level structure of 125Sb is discussed in terms of particle-core excitation coupling. With the help of empirical shell model calculations the three isomers are proposed to have three-quasiparticle πg7/2(*)V(h11/2s1/2)5-,πg7/2(*)V(h11/2d3/2)7-and πg7/2(*)V(h211/2)10+configurations, respectively.     

High-spin states of<Superscript>125</Superscript>Sb: Particle-core excitation coupling

Excited states of¹²⁵Sb have been studied using in-beam γ spectroscopy techniques via the¹²⁴Sn(⁷Li, α2n) reaction at a beam energy of 32 MeV. A high-spin level scheme including 21 new γ-transitions and 14 new excited states have been established. Three isomers have been identified at 1970, 2110 and 2471 keV and the ranges of their half-lives have been estimated from the delayed coincidence data. The level structure of¹²⁵Sb is discussed in terms of particle-core excitation coupling. With the help of empirical shell model calculations the three isomers are proposed to have three-quasiparticle πg_7/2⊗v(h _11/2 s _1/2)₅₋, πg_7/2⊗v(h _11/2 d _3/2)₇₋ and πg_7/2⊗v(h ₁₁^2/2)₁₀ ⁺ configurations, respectively.