利巴韦林、磷酸氯喹、盐酸阿比多尔等抗病毒药物的红外光谱表征

自新冠肺炎(COVID-19)疫情爆发以来,国内外多家研究机构和企业都在加快推进新冠病毒(SARS-CoV-2)抗体药物的研发。药物多晶型限制了有效药物的研发进度。药物生产、存储和使用环境影响了药物的稳定性。红外光谱作为一种快速无损检测手段,可从振动光谱反映出药物结构、晶型甚至生产工艺上的差异大大提高了研发效率。首次以三种临床试验被认为治疗新冠肺炎有效药物：磷酸氯喹,利巴韦林和盐酸阿比多尔为例,利用傅里叶红外光谱仪测试得到它们在远红外(1～10 THz)和中红外(400～4 000 cm-1)波段的振动光谱。远红外光谱中,利巴韦林的特征峰位于：2.01,2.68,3.37,4.05,4.83,5.45,5.92,6.42和7.14 THz附近;磷酸氯喹的特征峰位于：1.26,1.87,2.37,3.06,3.78,5.09和6.06 THz附近;盐酸阿比多尔的特征峰位于：2.24,3.14,3.72,4.25和5.38 THz附近。结合密度函理论,选择B3LYP杂化泛函和6-311++G(d,p)基组,利用Crystal14和Gaussian16软件分析了光谱中所有特征峰对应的振动模式,实现了对振动光谱的精确指认。远红外波段,振动模式源自分子的集体振动。中红外波段,2 800 cm-1以下,振动模式主要源自基团的面内外弯曲和摇摆;2 800 cm-1以上,振动模式过渡为C—H,O—H和N—H键的面内伸缩。以考虑了周期性边界条件的晶体结构作为理论计算的初始构型,会让理论光谱与实验光谱更加吻合,尤其是在远红外波段和中红外400～1 000 cm-1的低频段。该研究对深入理解磷酸氯喹,利巴韦林和盐酸阿比多尔等抗病毒药物的药学特性,药物间相互作用,控制药物生产过程,指导药物存储和使用有重大意义。     

Theoretical study of silicon–sulfur clusters (SiS2)n (n = 1–6)

 The possible geometrical structures and relative stability of (SiS₂) _n (n=1–6) silicon–sulfur clusters are explored by means of density functional theory quantum chemical calculations. The effects of polarization functions and electron correlation are included in these calculations. The electronic structures and vibrational spectra of the most stable geometrical structures of (SiS₂) _n are analyzed by the same method. As a result, the regularity of the (SiS₂) _n cluster growth is obtained, and the calculation may used for predicting the formation mechanism of the (SiS₂) _n cluster. Received: 17 November 1999 / Accepted: 3 November 2000 / Published online: 3 May 2001     

A theoretical study on the ionization of OCS with an analysis of vibrational structures of the photoelectron spectrum

 Ab initio calculations have been performed to study the molecular structures and vibrational levels of the four low-lying ionic states (1, 2²Π, and 1, 2²Σ⁺) of carbonyl sulfide. The global regions of the potential-energy surfaces have been obtained by multireference single and double excitation configuration interaction calculations. Vibrational calculations using explicit vibrational Hamiltonians have been used for vibrational analysis. The equilibrium molecular structures and a vibrational analysis of the four ionic states are presented. The theoretical ionization intensity curves including the vibrational structures of the ionic states are also presented and are compared with the photoelectron spectrum. Received: 20 January 2001 / Accepted: 22 August 2001 / Published online: 30 October 2001     

Equilibrium bond lengths, force constants and vibrational frequencies of MnF2, FeF2, CoF2, NiF2, and ZnF2 from least-squares analysis of gas-phase electron diffraction data

The least-squares analysis of the electron diffraction data for MnF₂, FeF₂, CoF₂, NiF₂ and ZnF₂ was carried out in terms of a cubic potential function. The obtained equilibrium bond lengths (in Å) are r_e(Mn–F)=1.797(6), r_e(Fe–F)=1.755(6), r_e(Co–F)=1.738(6), r_e(Ni–F)=1.715(7), and r_e(Zn–F)=1.729(7). The determined force constants and the corresponding vibrational frequencies are listed. The bond length r_e(Cu–F)=1.700(14) Å for CuF₂ was estimated and the variations of bond lengths for the first-row transition metal difluorides were discussed in light of their electronic structure.     

Sensitive determination of 3-methoxy-4-hydroxyphenylglycol (MHPG) in human plasma by HPLC with electrochemical detection

Summary This study deals with the development of a new HPLC method for the determination of 3-methoxy-4-hydroxyphenylglycol (MHPG), the main noradrenaline metabolite in human plasma. A Varian reversed-phase column (C₈; 250 mm×4.6 mm i.d.; 5 μm particles) was used as the stationary phase and an aqueous solution of citric acid, 1-octanesulfonic acid, EDTA, and methanol was used as the mobile phase. Coulometric electrochemical detection (ED) was used to obtain the highest sensitivity. Isolation of MHPG from plasma was accomplished by means of a new solid-phase extraction procedure after a protein precipitation step. The extraction yield of MHPG from plasma was very high (>97%). Linearity was observed in the 0.5–25 ng mL⁻¹ concentration range; the limit of detection was 0.2 ng mL⁻¹ and the limit of quantitation was 0.5 ng mL⁻¹. Repeatability (RSD,%) for plasma samples was found to be <3.2% and intermediate precision was <4.3%. The method was applied to the determination of MHPG in the plasma of healthy subjects under experimentally-induced psychological stress.     

Rotational bands in the doubly odd 130Cs nucleus

The band structures built on the 5^- isomeric state ( T _1/2 = 3.46 m) in the doubly odd ¹³⁰Cs nucleus have been established up to I = 24? via the ¹²⁴Sn(¹¹B, 5n)¹³⁰Cs reaction. The previously observed bands based on the πh _11/2⊗νh _11/2, πg _7/2⊗νh _11/2 and πd _5/2⊗νh _11/2 configurations and a positive-parity side band with multiple connections to the α = 0 signature partner of the yrast πh _11/2⊗νh _11/2 band have been extended to higher spins. A new band based on the πh _11/2⊗νg _7/2 configuration is observed. The yrast πh _11/2⊗νh _11/2 band exhibits anomalous signature splitting whose magnitude decreases up to spin 15 and then increases without restoring the normal signature splitting. Received: 20 February 2001 / Accepted: 9 May 2001     

High-spin states in the 96Tc nucleus

High-spin states in the ⁹⁶Tc nucleus have been studied with the reactions ⁸²Se(¹⁹F,5nγ) at 68 MeV and Zn(³⁶S,αpxn) at 130 MeV. Two γ-ray cascades (irregular bandlike structures) have been observed up to an excitation energy of about 10 MeV and spin 21-22?. Received: 19 January 2001 / Accepted: 30 March 2001     

High-spin states in 160Lu

High-spin states of ¹⁶⁰Lu have been studied through the ¹⁴⁴Sm( ¹⁹F, 3n) reaction. The previously known πh _11/2⊗υi _13/2 yrast band is extended from I ^π = 21^- to 25^- and a four quasiparticle band with configuration πh _11/2[523]7/2 ^-⊗υh _9/2[521]3/2 ^-⊗ (υi _13/2)² is reported. Received: 21 May 2001 / Accepted: 19 July 2001     

The halo of the exotic nucleus 11Li: a single Cooper pair

If neutrons are progressively added to a normal nucleus, the Pauli principle forces them into states of higher momentum. When the core becomes neutron saturated, the nucleus expels most of the wave function of the last neutrons outside to form a halo, which, because of its large size, can have a lower momentum. It is an open question how nature stabilizes such a fragile system and provides the glue needed to bind the halo neutrons to the core. Here, we show that this problem is similar to that of the instability of the normal state of an electron system at zero temperature solved by Cooper, a solution which is at the basis of BCS theory of superconductivity. By mimicking this approach using, aside from the bare nucleon-nucleon interaction, the long wavelength vibrations of the nucleus ¹¹Li, the paradigm of halo nuclei, as tailored glues of the least bound neutrons, we are able to obtain a unified and quantitative picture of the observed properties of ¹¹Li. Received: 9 May 2001 / Accepted: 17 November 2001     

New excited superdeformed bands in heavy Pb nuclei: Clue for an octupole softness near the N = 118 gap at large deformation

We report the identification of six new superdeformed (SD) bands in ^197,198Pb observed with the EUROBALL IV spectrometer. The results are interpreted in the framework of cranked Hartree-Fock calculations with approximate projection on the particle number by means of the Lipkin-Nogami method. A mixing between quasi-particle excitations and an octupole vibration is suggested in the two SD isotopes. We have estimated the ordering of the neutron valence orbitals and confirm indirectly a N = 118 SD gap. Received: 20 December 2000 / Accepted: 24 January 2001