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Synthesis and Alkali-Metal-Ion Complexation of P-Stereogenic Diphosphacrowns.

ABSTRACT: Phosphine is conformationally stable because of the high inversion energy barrier of the phosphorus atom, which allows the phosphorus atom to become a chiral center. Thus, enantiopure P-stereogenic 12-, 15-, 18-, and 21-membered aliphatic phosphines "diphosphacrowns" were synthesized from secondary P-stereogenic bisphosphine as a chiral building block. Their complexation behaviors with alkali metal ions are investigated in comparison with benzo-18-diphosphacrown-6 and benzo-18-crown-6. 15-, 18-, and 21-Membered diphosphacrowns captured alkali metal ions to form 1:1 metal complexes. Unique guest selectivity was observed, as diphosphacrowns encapsulated smaller alkali metal ions than common crown ethers; for example, 18-membered diphosphacrowns interacted more strongly with Na(+) than K(+). The difference in guest selectivity between diphosphacrowns and common crown ethers is speculated to result from the cavity size, owing to the large phosphorus atom as well as steric hindrance around the phosphine moiety.

SUBMITTER: Morisaki Y

PROVIDER: S-EPMC4981053 | biostudies-literature | 2016 Aug

REPOSITORIES: biostudies-literature

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Synthesis and Alkali-Metal-Ion Complexation of P-Stereogenic Diphosphacrowns.

Morisaki Yasuhiro Y Kato Ryosuke R Chujo Yoshiki Y

ChemistryOpen 20160602 4

Phosphine is conformationally stable because of the high inversion energy barrier of the phosphorus atom, which allows the phosphorus atom to become a chiral center. Thus, enantiopure P-stereogenic 12-, 15-, 18-, and 21-membered aliphatic phosphines "diphosphacrowns" were synthesized from secondary P-stereogenic bisphosphine as a chiral building block. Their complexation behaviors with alkali metal ions are investigated in comparison with benzo-18-diphosphacrown-6 and benzo-18-crown-6. 15-, 18-, ...[more]

PMID: 27547642

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Project description:Drug adulteration and contamination are serious threats to human health therefore, their accurate monitoring is very important. Allopurinol (Alp) and theophylline (Thp) are commonly used drugs for the treatment of gout and bronchitis, while their isomers hypoxanthine (Hyt) and theobromine (Thm) have no effect and affect the efficacy of the drug. In this work, the drug isomers of Alp/Hyt and Thp/Thm are simply mixed with α-, β-, γ-cyclodextrin (CD) and metal ions and separated using trapped ion mobility spectrometry-mass spectrometry (TIMS-MS). TIMS-MS results showed that Alp/Hyt and Thp/Thm isomers could interact with CD and metal ions and form corresponding binary or ternary complexes to achieve their TIMS separation. Different metal ions and CDs showed different separation effect for the isomers, among which Alp and Hyt could be successfully distinguished from the complexes of [Alp/Hyt+γ-CD + Cu–H]+ with separation resolution (RP–P) of 1.51; whereas Thp and Thm could be baseline separated by [Thp/Thm+γ-CD + Ca–H]+ with RP–P of 1.96. Besides, chemical calculations revealed that the complexes were in the inclusion forms, and microscopic interactions were somewhat different, making their mobility separation. Moreover, relative and absolute quantification was investigated with an internal standard to determine the precise isomers content, and good linearity (R2 > 0.99) was obtained. Finally, the method was applied for the adulteration detection where different drugs and urine were analyzed. In addition, due to the advantages of fast speed, simple operation, high sensitivity, and no chromatographic separation required, the proposed method provides an effective strategy for the drug adulteration detection of isomers. Graphical abstract Image 1 Highlights • Alp/Thp and Hyt/Thm isomers were analyzed by ion mobility.• Alp/Hyt were distinguished by [Alp/Hyt+γ-CD + Cu–H]+ with Rp-p of 1.51.• Thp/Thm was baseline separated by [Thp/Thm+γ-CD + Ca–H]+ with Rp-p of 1.96.• Quantification for the isomers was measured with internal standard.• Alp/Hyt and Thp/Thm drugs were adulteration analysis in drugs and urine.

Dataset Information

Synthesis and Alkali-Metal-Ion Complexation of P-Stereogenic Diphosphacrowns.

Publications

Synthesis and Alkali-Metal-Ion Complexation of P-Stereogenic Diphosphacrowns.

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