Four Metal Complexes Based on Bulky Imidazole Ligands: Solvothermal Syntheses,Crystal Structures,and Fluorescence Properties

In order to explore the influences of (de‐)protonation of the imidazole ring on the structural diversity of the resulting complexes, the imidazole‐based ligands 4, 5‐diphenylimidazole (Hdpi) and 1H‐phenanthro[9, 10‐d]imidazole (Hpi) were utilized as bulky building blocks to construct four complexes by solvothermal reactions, i.e. [Ag(Hdpi)₂](NO₃) · (H₂O) ( 1 ), [Cu(dpi)]_∞ ( 2 ), [Cu(Hpi)(NO₃)]_∞ ( 3 ), and [(H₂pi)(NO₃)] · H₂O ( 4 ). In complex 1 , two Hdpi ligands adopt a monodentate pattern and coordinate with one Ag^I ion to form a mononuclear unit, which is further connected by hydrogen bonds into a 1D supramolecular helix. The deprotonated dpi ligand of 2 acts in bidentate mode, and bridges Cu^I ions to afford a 1D chain. In 3 , the NO₃^– ion, acts as a monodentate bridging ligand and joins Cu^I ions to generate a 1D chain. The Hpi ligand employs a monodentate mode to bond with Cu^I ions of the 1D chain. 4 is protonated and two H₂pi nitrogen atoms are free of coordination. Interestingly, hydrogen bonds among the NO₃^– ion, the H₂pi ligand, and the water molecule yield a macro ring R⁴₄(14). The resulting structural diversity reveals that the (de‐)protonation of imidazole ring directly steers the coordination number of ligand, and thus causes a significant effect on the structure, especially the dimensionality. Furthermore, the solid‐state fluorescence properties of the free ligands and compounds 1 – 4 were studied at room temperature.     

A comparative study of HPLC-UV and UPLC-DAD methods for simultaneous estimation of aspirin and cilostazol in the presence of their related impurities in bulk and capsules

Aspirin (ASP) and cilostazol (CST) are used as a combination in pharmaceutical formulations for treatment of strokes. Salicylic acid (SAL) is considered to be one of the main synthesis impurities and a degradation product of ASP. On the other hand, the main related impurities of CST are CST related A, B, and C (CST-RA, CST-RB, and CST-RC), respectively. Furthermore, as high efficiency and less elution are the basic requirements of high-speed chromatographic separation, so, a comparative study of two simple, precise, and accurate reversed-phase HPLC and UPLC methods was developed and validated for simultaneous estimation of ASP and CST in bulk and capsules in the presence of SAL, CST-RA, CST-RB, and CST-RC. A Eurospher II C18 (250?×?4.6?mm², 5?µm) for HPLC method and an Agilent Zorbax Eclipse Plus C18 (50?×?2.1?mm², 1.8?µm) for UPLC method were used. A gradient mobile phase of 20?mM anhydrous KH₂PO₄ buffer solution (containing 0.2% triethylamine (TEA), v/v) with pH adjusted to 2.9 using orthophosphoric acid (solution A) and acetonitrile (solution B) mixed in different proportions for HPLC and UPLC methods was prepared. Flow rate was set to 1.0 and 0.3?mL min^?1 for HPLC and UPLC methods, respectively, and the detection was performed for both methods at 210?nm. It worth noting that the proposed UPLC-DAD assay exhibited relatively much more precision, sensitivity, specificity, and economic and chromatographic separation superiority than proposed HPLC-UV assay. Both developed methods were compared with reference methods to prove its applicability and are suitable for purity assessment of ASP and CST in bulk and capsules.     

Two Zn(II)‐based meta‐organic frameworks: Selective detection of antibiotics and treatment activity on age‐related macular degeneration by reducing inflammasome activation

Via utilizing the mixed‐ligand method, two novel Zn(II)‐containing meta‐organic frameworks with the chemical formula of {[Zn(L)(5‐HIP)]·H₂O}_n ( 1 ) and [Zn(L)(2,6‐NDC)]_n ( 2 ) were prepared under the solvothermal conditions by applying aromatic dicarboxylic acids ligands (5‐H₂HIP = 5‐hydroxyisophthalic acid; 2,6‐H₂NDC = 2,6‐naphthalenedicarboxylic acid) and 1,4‐bis(benzimidazol‐1‐yl)‐2‐butylene (L). Due to its good water stability as well as the strong luminescent emission around room temperature, complex 2 has the high selectivity and sensibility of fluorescence detection to the ceftriaxone sodium (a kind of antibiotic) with the detection limit up to ppm lever. The treatment activity of the compounds on age‐related macular degeneration was assessed and the specific mechanism was investigated. First of all, the inflammasome activation in the endothelial cells of retina was evaluated with western blot. In addition to this, the down‐stream production of the inflammasome activation was also measured with ELISA detection kit.     

Favipiravir (SARS-CoV-2) degradation impurities: Identification and route of degradation mechanism in the finished solid dosage form using LC/LC–MS method

Favipiravir finished dosage was approved for emergency use in many countries to treat SARS-CoV-2 patients. A specific, accurate, linear, robust, simple, and stability-indicating HPLC method was developed and validated for the determination of degradation impurities present in favipiravir film-coated tablets. The separation of all impurities was achieved from the stationary phase (Inert sustain AQ-C18, 250 × 4.6 mm, 5-μm particle) and mobile phase. Mobile phase A contained KH₂PO₄ buffer (pH 2.5 ± 0.05) and acetonitrile in the ratio of 98:2 (v/v), and mobile phase B contained water and acetonitrile in the ratio of 50:50 (v/v). The chromatographic conditions were optimized as follows: flow rate, 0.7 mL/min; UV detection, 210 nm; injection volume, 20 μL; and column temperature, 33°C. The proposed method was validated per the current International Conference on Harmonization Q2 (R1) guidelines. The recovery study and linearity ranges were established from the limit of quantification to 150% optimal concentrations. The method validation results were found to be between 98.6 and 106.2% for recovery and r² = 0.9995–0.9999 for linearity of all identified impurities. The method precision results were achieved below 5% of relative standard deviation. Forced degradation studies were performed in chemical and physical stress conditions. The compound was sensitive to chemical stress conditions. During the study, the analyte degraded and converted to unknown degradation impurities, and its molecular mass was found using the LC–MS technique and established degradation pathways supported by reaction of mechanism. The developed method was found to be suitable for routine analysis of research and development and quality control.     

定量开采条件下径向渗流的液固耦合问题

考虑到多孔介质渗透率随孔隙度变化的特点，建立了力学模型，研究定量抽放问题；对于广义平面应力状态下的非线性渗流耦合问题，提出了解的构造方法和解耦方法；求出了耦合条件下的孔隙压力，多孔介质总应力、总应变和总位移的解析解；进行了实例计算，并与Biot理论进行了对比，结果表明两种理论的差别很大。因此在渗透系数有较明显变化的场舍下不能采用Biot理论进行分析。     

On Convergence of Quasi ρ-preserving Locally Related Quasi-nonexpansive Mappings

The concept of quasi-nonexpansive mappings was initiated in Diaz and Metcalf (Bull. Amer. Math. Soc. 73 (1967), 516–519), further it was generalized by Petryshyn and Williamson (Journal of Mathematical Analysis and Applications 43, no. 2 (1973): 459-497). Further investigating the above work, in this article a Banach space with a relation ρ has been considered, the notion of ρ-preserving and quasi ρ-preserving locally related quasi-nonexpansive mappings has been introduced. It has been shown that every ρ-preserving mapping is a quasi ρ-preserving and every nonexpansive mapping is locally related quasi-nonexpansive but converse may not hold. The necessary and sufficient conditions for the convergence of Picard, Mann and Ishikawa iterations of ρ-preserving, quasi ρ-preserving locally related quasi-nonexpansive mappings are presented.     

A study on small-world brain functional networks altered by postherpetic neuralgia

Understanding the effect of postherpetic neuralgia (PHN) pain on brain activity is important for clinical strategies. This is the first study, to our knowledge, to relate PHN pain to small-world properties of brain functional networks. Functional magnetic resonance imaging (fMRI) was used to construct functional brain networks of the subjects during the resting state. Sixteen patients with PHN pain and 16 (8 males, 8 females for both groups) age-matched controls were studied. The PHN patients exhibited decreased local efficiency along with non-significant changes of global efficiency in comparison with the healthy controls. Moreover, regional nodal efficiency was found to be significantly affected by PHN pain in the areas related to sense (postcentral gyrus, inferior parietal gyrus and thalamus), memory/affective processes (parahippocampal gyrus) and emotional activities (putamen). Significant correlation (p < 0.05) was also found between the nodal efficiency of putamen and pain intensity in PHN patients. Our results suggest that PHN modulates the local efficiency, and the small-world properties of brain networks may have potentials to objectively evaluate pain information in clinic.     

Maximum likelihood estimation for second level fMRI data analysis with expectation trust region algorithm

The trust region method which originated from the Levenberg–Marquardt (LM) algorithm for mixed effect model estimation are considered in the context of second level functional magnetic resonance imaging (fMRI) data analysis. We first present the mathematical and optimization details of the method for the mixed effect model analysis, then we compare the proposed methods with the conventional expectation-maximization (EM) algorithm based on a series of datasets (synthetic and real human fMRI datasets). From simulation studies, we found a higher damping factor for the LM algorithm is better than lower damping factor for the fMRI data analysis. More importantly, in most cases, the expectation trust region algorithm is superior to the EM algorithm in terms of accuracy if the random effect variance is large. We also compare these algorithms on real human datasets which comprise repeated measures of fMRI in phased-encoded and random block experiment designs. We observed that the proposed method is faster in computation and robust to Gaussian noise for the fMRI analysis. The advantages and limitations of the suggested methods are discussed.