Tandem mass spectrum of a growth hormone secretagogue: Amide bond cleavage and resultant gas-phase rearrangement

Compound 1 [N-[1(R)-[(1,2-dihydro-1-methylsulfonylspiro[3H-indole-3,4'-piperidin]-1'-yl)carbonyl]-2-(phenylmethyloxy)ethyl]-2-amino-2-methylpropanamide](MW 528) is an orally-active growth hormone secretagogue (GHS). As part of a continual effort to analyze the ESI/MS and MSn data of novel drugs, the ESI/MS and MS/MS data of protonated 1 (m/z 529) are analyzed and reported here. The analyses reveal that under low-energy collision-induced dissociation (CID) in an ion trap or a quadrupole collision cell, protonated 1 undergoes a gas-phase rearrangement to form protonated 3 (m/z 357) which competes with the y- and b-type product ions during the amide bond cleavages of protonated 1. It is proposed that when the b-type ion is formed by cleavage of the piperidine amide bond, piperidine (a neutral species) and the b-ion (a cation) form an ion-neutral complex. In this complex, piperidine functions as a nucleophile to attack the benzylic carbon of the b-ion, and the protonated ether group in the b-ion acts as a leaving group, which results in the migration of the benzylic group to the piperidine amine to form protonated 3. Protonated 2 (an analog of 1) was studied under the same experimental conditions. The results show that protonated 2 undergoes a similar rearrangement to form protonated 3. While this rearrangement is a relatively minor fragmentation process for protonated 1, it is a predominant process for protonated 2. This phenomenon is explained in terms of the proposed ion-neutral-complex mechanism.     

高效液相色谱法测定忍冬藤和叶中8种活性成分

建立了多波长分析忍冬藤和叶中化学成分含量的高效液相色谱分析方法,色谱柱为Aglient Zorbax80A,Extend-C18(4.6mm×250mm,5μm);流动相为0.3%甲酸-乙腈,梯度洗脱;流速为1.5mL/min;检测波长为240、330、360nm;柱温38℃。各指标成分的检出限均低于0.29mg/L;精密度RSD均低于2.29%;标准加入的回收率为91.2%～103.6%。应用新建立的方法测定了7个不同产地忍冬藤和叶中8种活性成分的含量。该方法简单、快速、准确,可用于忍冬藤和叶的质量控制。     

2,6-二氯靛酚钠动力学分光光度法测定西红柿及草莓中的抗坏血酸

本文提出用2，6－二氯靛酚纳（以下简写DIS）作氧化剂动力学分光光度测定L－抗坏血酸的新方法。DIS与L－抗坏血酸混合．在固定时间间隔于611nm处测得吸光度A值的变化（△A／△t）与抗坏血酸含量成线性关系。线性范围为0～12mg／L。在样品处理时采用偏磷酸作为提取剂，以减缓抗坏血酸被氧化的速度结果表明，该方法有较高灵敏度，且操作简便，试剂易得，容易推广，是测定水果和蔬菜中L-抗坏血酸的好方法。     

12-钨磷酸希土盐DMF、DMSO加合物的合成、性质及其热分解动力学常数研究

合成了8种钨磷酸希土盐LnPW₁₂O₄₀·xH₂O(Ln=Y、La、Nd、Sm、Gd、Dy、Ho、Yb)的DMF、DMSO加合物,对加合物进行了组成分析,通过IR光谱、TG-DTA曲线对加合物进行了性质表征,并着重研究了加合物热分解过程的动力学,给出了热分解反应级数n和活化能E.     

FT-IR evidence for the participation of protonic sites in the heterolytic cleavage of C?H bonds of methane over HZSM-5 zeolite

It has been observed by FT-IR spectroscopy that both kinds of Brönsted acid protons present in HZSM-5 zeolite may be involved in the adsorption of methane at low temperature (173 K) and exchange with CH₄ or CD₄ at high temperature (>500°C). The sites which can adsorb methane at low temperature are the active sites for methane conversion at high temperature. Over HZSM-5 zeolite, the activation of methane is suggested to occur via a heterolytic cleavage of C–H bond with the assistance of protons.     

热缓冲剂对稀土贮氢合金吸氢动力学的影响

以铜粉作为热缓冲剂添加到稀土贮氢合金粉中,应用动力学机理函数计算机拟合的方法,研究了ML(NiCoMnAlCu)5和Mm(NiCoMnAlCu)5(ML为富镧混合稀土金属,Mm为富铈混合稀土金属)在α+β相区恒温吸氢动力学.研究结果表明,当铜粉与贮氢合金粉达到一定比例时,能够消除热传导对吸氢动力学的影响.富铈稀土合金和富镧稀土合金吸氢均受氢在β相的内扩散控制,合金中随La/Ce比例的减小,吸氢速度加快.     

流动注射微柱预分离富集荧光光度法测定肥料中的铈

用抗坏血酸将Ce(Ⅳ)还原为Ce(Ⅲ),以多聚磷酸钠作为增强剂,建立了铈的流动注射荧光分析法,考查了各种因素对测定Ce的影响.此方法线性范围为2.0×10-9～1.2×10-8 g·ml-1.采用流动注射微柱预分离富集测定了GBW07602标样和氨基酸微肥中的铈含量.测定结果与推荐值有良好的一致性.     

Microwave assisted hydrothermal synthesis of tin niobates nanosheets with high cycle stability as lithium-ion battery anodes

SnNb₂O₆ and Sn₂Nb₂O₇ nanosheets were synthetized via microwave assisted hydrothermal method, and innovatively employed as anode materials for lithium-ion battery. Compared with Sn₂Nb₂O₇ and the previously reported pure Sn-based anode materials, the SnNb₂O₆ electrode exhibited outstanding cycling performance.     

Regioselective synthesis of 1,2,3-triazole derivatives via 1,3-dipolar cycloaddition reactions in water

Reaction of an arylacetylene with an azide in hot water gave 1,4-disubstituted 1,2,3-triazoles in high yields, while similar reaction between a terminal aliphatic alkyne and an azide (except m-nitroazidobenzene) afforded a mixture of regioisomers with the ratio of 1,4- to 1,5-isomers ranging from 3:1 to 28.6:1. Reactions of m-nitroazidobenzene with either arylalkynes or aliphatic alkynes formed only 1,4-disubstituted derivatives in excellent yields.     

Synthesis of N—（4—Salicylideneiminoaryl）monoaza Crown Ethers and Dioxygen Affinities of Their Cobalt（Ⅱ）Complexes

The Schiff base‐containing pendant monoaza crown ether HL¹, HL², HL³ and HL⁴ have been synthesized by condensation of salicylaldehyde with N‐(4‐aminoaryl) monoaza crown ethers, which were prepared conveniently from 4‐nitro‐N, N‐di(hydroxyethyl) aniline or 4‐nitrobenzyl chloride via cyclization or condensation and reduction. The structures of HL¹—HL⁴ were verified by ¹H NMR, IR spectra, MS and elemental analysis. Moreover, the oxygenation constants (KO2) and thermodynamic parameters (δH⁰ and δS⁰) of their cobalt(II) complexes were determined in the range of ?5 °C to 25 °C, and the effect of crown ring bonded to a Schiff base on the dioxygen affinities of cobalt(II) complexes was also observed as compared to the uncrowned analogue (CoL).