A gadolinium-based magnetic ionic liquid for supramolecular dispersive liquid–liquid microextraction followed by HPLC/UV for the determination of favipiravir in human plasma

Favipiravir is a potential antiviral medication that has been recently licensed for Covid-19 treatment. In this work, a gadolinium-based magnetic ionic liquid was prepared and used as an extractant in dispersive liquid–liquid microextraction (DLLME) of favipiravir in human plasma. The high enriching ability of DLLME allowed the determination of favipiravir in real samples using HPLC/UV with sufficient sensitivity. The effects of several variables on extraction efficiency were investigated, including type of extractant, amount of extractant, type of disperser and disperser volume. The maximum enrichment was attained using 50 mg of the Gd-magnetic ionic liquid (MIL) and 150 μl of tetrahydrofuran. The Gd-based MIL could form a supramolecular assembly in the presence of tetrahydrofuran, which enhanced the extraction efficiency of favipiravir. The developed method was validated according to US Food and Drug Administration bioanalytical method validation guidelines. The coefficient of determination was 0.9999, for a linear concentration range of 25 to 1.0 × 10⁵ ng/ml. The percentage recovery (accuracy) varied from 99.83 to 104.2%, with RSD values (precision) ranging from 4.07 to 11.84%. The total extraction time was about 12 min and the HPLC analysis time was 5 min. The method was simple, selective and sensitive for the determination of favipiravir in real human plasma.     

A microfluidics-dispensing-printing strategy for Janus photonic crystal microspheres towards smart patterned displays

From the implementation point of view, the printable magnetic Janus colloidal photonic crystals (CPCs) microspheres are highly desirable. Herein, we developed a dispensing-printing strategy for magnetic Janus CPCs display via a microfluidics-automatic printing system. Monodisperse core/shell colloidal particles and magnetic Fe₃O₄ nanoparticles precursor serve as inks. Based on the equilibrium of three-phase interfacial tensions, Janus structure is successfully formed, followed by UV irradiation and self-assembly of colloid particle to generate magnetic Janus CPCs microspheres. Notably, this method shows distinct superiority with highly uniform Janus CPCs structure, where the TMPTA/Fe₃O₄ hemisphere is in the bottom side while CPCs hemisphere is in the top side. Thus, by using Janus CPCs microspheres with two different structural colors as pixel points, a pattern with red flower and green leaf is achieved. Moreover, 1D linear Janus CPCs pattern encapsulated by hydrogel is also fabricated. Both the color and the shape can be changed under the traction of magnets, showing great potentials in flexible smart displays. We believe this work not only offers a new feasible pathway to construct magnetic Janus CPCs patterns by a dispensing-printable fashion, but also provides new opportunities for flexible and smart displays.     

Lanthanide SMMs Based on Belt Macrocycles: Recent Advances and General Trends

Enhancement of axial magnetic anisotropy is the central objective to push forward the performance of Single-Molecule Magnet (SMM) complexes. In the case of mononuclear lanthanide complexes, the chemical environment around the paramagnetic ion must be tuned to place strongly interacting ligands along either the axial positions or the equatorial plane, depending on the oblate or prolate preference of the selected lanthanide. One classical strategy to achieve a precise chemical environment for a metal centre is using highly structured, chelating ligands. A natural approach for axial-equatorial control is the employment of macrocycles acting in a belt conformation, providing the equatorial coordination environment, and leaving room for axial ligands. In this review, we present a survey of SMMs based on the macrocycle belt motif. Literature systems are divided in three families (crown ether, Schiff-base and metallacrown) and their general properties in terms of structural stability and SMM performance are briefly discussed.     

Functional Groups Assisted Tunable Dielectric Permittivity of Guest-Free Zn-Based Coordination Polymers for Gate Dielectrics

The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH₂) and electron-withdrawing (R=NO₂) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L₁)(L₂)]_n ( 1 ) and [Zn(L₁)(L₃)]_n ( 2 ) [L₁=2-(2-pyridyl) benzimidazole (Pbim), L₂=5-aminoisophthalate (Aip), and L₃=5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH₂ and NO₂ substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO₂ and NH₂. Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties.     

基于多材质复合管柱的裸眼井壁支撑工艺及应用

已完钻超深裸眼水平井侧钻技术是经济、高效开发油藏剩余油的主要手段之一，传统的磨铣钢套管开窗侧钻技术存在下入摩阻大、磨铣耗时长导致开窗失败等问题。为此，提出了基于多材质复合管柱的超深水平井裸眼井壁支撑工艺，结合中国西北油田已完钻超深裸眼水平井井况，首先，提出了基于“铝合金+碳钢”的多材质复合管柱组合及设计方法；其次，开展了基于管柱实物屈曲实验数据的管柱临界屈曲载荷计算模型适用性评价，并优选出了适合于“铝合金+碳钢”多材质复合管柱的屈曲临界载荷计算模型；最后，研究了综合考虑管柱扭矩、摩阻、刚性、井眼条件、管柱强度及材质的多材质复合管柱下入性分析方法，并利用下入性分析软件对西北油田顺北X1井、X2井、X3井、X4井复合管柱进行了下入可行性评价。该方法在X1井和X2井得到成功应用，进一步论证了该工艺现场应用的可行性。研究成果可为超深水平井裸眼井壁支撑的复合管柱设计和下入可行性评价提供理论参考。     

High-fidelity Recognition of Organotrifluoroborate Anions (R−BF3−) as Designer Guest Molecules

The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF₃⁻). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF₃⁻, by cyanostar macrocycles that are size-complementary to the inorganic BF₄⁻ progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K⁺ salts of R−BF₃⁻ anions.     

Pattern transition and regulation in a subthalamopallidal network under electromagnetic effect

Although the significant roles of magnetic induction and electromagnetic radiation in the neural system have been widely studied, their influence on Parkinson's disease (PD) has yet to be well explored. By virtue of the magnetic flux variable, this paper studies the transition of firing patterns induced by magnetic induction and the regulation effect of external magnetic radiation on the firing activities of the subthalamopallidal network in basal ganglia. We find: (i) The network reproduces five typical waveforms corresponding to the severity of symptoms: weak cluster, episodic, continuous cluster, episodic, and continuous wave. (ii) Magnetic induction is a double-edged sword for the treatment of PD. Although the increase of magnetic coefficient may lead the physiological firing activity to transfer to pathological firing activity, it also can regulate the pathological intensity firing activity with excessive β-band power transferring to the physiological firing pattern with weak β-band power. (iii) External magnetic radiation could inhibit continuous tremulous firing and β-band power of subthalamic nucleus (STN), which means the severity of symptoms weakened. Especially, the bi-parameter plane of the regulation region shows that a short pulse period of magnetic radiation and a medium level of pulse percentage can well regulate pathological oscillation. This work helps to understand the firing activity of the subthalamopallidal network under electromagnetic effect. It may also provide insights into the mechanisms behind the electromagnetic therapy of PD-related firing activity.