Determination of four acidic nonsteroidal anti‐inflammatory drugs in wastewater samples by dispersive liquid–liquid microextraction based on solidification of floating organic droplet and high‐performance liquid chromatography

A simple, environmentally friendly, and sensitive dispersive liquid–liquid microextraction based on solidification of floating organic droplet for the extraction of four acidic nonsteroidal anti‐inflammatory drugs (ketoprofen, naproxen, ibuprofen, and diclofenac) from wastewater samples subsequent by high‐performance liquid chromatography analysis was developed. The influence of extraction parameters such as pH, the effect of solution ionic strength, type of extraction solvent, disperser solvent, and extraction solvent volume were studied. High enrichment factors (283–302) were obtained through the developed method. The method provides good linearity (r > 0.999) in a concentration range of 1–100 μg/L, good intra‐ and inter‐day precision (relative standard deviation < 7%) and low limits of quantification. The relative recoveries of the selected compounds were situated over 80% both in synthetic and real water samples. The developed method has been successfully applied for the analysis of the selected compounds in wastewater samples.     

Coumarinolignans Isolated from the Seeds of Brucea javanica

A new coumarinolignan, cleomiscosin E ( 1 ), together with the known compound cleomiscosin A ( 2 ), has been isolated from the seeds of Brucea javanica (L.) Merr . Their structures were assigned on the basis of spectral studies. These two compounds exhibited potent anti‐inflammatory activities by inhibiting the nitric oxide (NO) production in lipopolysaccharide (LPS)‐activated RAW264.7 macrophages.     

Determination of acidic drugs in biological and environmental matrices by membrane‐based dual emulsification liquid‐phase microextraction followed by high‐performance liquid chromatography

A simple method is introduced providing a highly clean microextraction for the determination of some anti‐inflammatory drugs as the model analytes in human urine and environmental matrices. This method is based upon the implementation of two consecutive emulsification liquid‐phase microextractions, which are separated by a syringe filtration step. In this method, the organic extraction solvent (dihexyl ether) is dispersed into the aqueous sample solution (20 mL), and the resulting cloudy mixture is passed through a hydrophilic polytetrafluoroethylene syringe filter. By this action, the extraction phase containing the analytes and many interfering species that could be transferred into the organic phase is retained behind the hydrophilic membrane. The filter is then detached from the syringe and attached to another syringe containing an aqueous solution (pH 12.0, 150 μL), and by the in‐syringe dispersion of the organic phase into the aqueous phase, the analytes are selectively back‐extracted into the aqueous phase. The developed method is centrifuge‐free and very simple, and provides a high sample clean‐up in a few minutes. Under the optimized experimental conditions, the developed method provided a linearity in the range of 2.0–2000 ng/mL, a low limit of detection (0.5 ng/mL), and enrichment factors of 47–53.     

微波辅助萃取-高效液相色谱法检测动物组织和牛奶中喹诺酮及非甾体类化合物

本文建立了一种快速的微薄辅助萃取-高效液相色谱法分离检测羊肝、牛肉和牛奶样品中三种喹诺酮类药物（氟罗沙星、洛美沙星和斯帕沙星）和两种非甾类化合物(酮洛芬和布洛芬)的方法。并对微波辅助萃取条件利用正交试验进行了优化：萃取温度为4℃、萃取时间为6min、萃取溶剂为乙腈、萃取溶剂体积为10mL。在浓度范围为0.25—0.75 μg•g－1时各待测物的三种不同水平的添加回收率在60.0%到107%之间,并获得较好的精确度（RSD＜11%）。     

A new antibacterial silver(I) complex incorporating 2,5‐dimethylpyrazine and the anti‐inflammatory diclofenac

Ag^I‐containing coordination complexes have attracted attention because of their photoluminescence properties and antimicrobial activities and, in principle, these properties depend on the nature of the structural topologies. A novel two‐dimensional silver(I) complex with the anti‐inflammatory diclofenac molecule, namely bis{μ‐2‐[2‐(2,6‐dichloroanilino)phenyl]acetato‐κ³O,O′:O}bis(μ‐2,5‐dimethylpyrazine‐κ²N:N′)silver(I), [Ag₂(C₁₄H₁₀Cl₂NO₂)₂(C₆H₈N₂)]_n, (I), has been synthesized and characterized by single‐crystal X‐ray diffraction, revealing that the Ag^I ions are chelated by the carboxylate groups of the anionic 2‐[2‐(2,6‐dichloroanilino)phenyl]acetate (dicl) ligand in a μ₃‐η¹:η² coordination mode. Each dicl ligand links three Ag^I atoms to generate a one‐dimensional infinite chain. Adjacent chains are connected through 2,5‐dimethylpyrazine (dmpyz) ligands to form a two‐dimensional layer structure parallel to the crystallographic bc plane. The layers are further connected by C—H…π interactions to generate a three‐dimensional supramolecular structure. Additionally, the most striking feature is that the structure contains an intramolecular C—H …Ag anagostic interaction. Furthermore, the title complex has been tested for its in vitro antibacterial activity and is determined to be highly effective on the studied microorganisms.     

Design of original bioactive formulations based on sugar-surfactant/non-steroidal anti-inflammatory catanionic self-assemblies: a new way of dermal drug delivery

A new kind of catanionic assembly was developed that associates a sugar-based surfactant with a non-steroidal anti-inflammatory drug (NSAID). Three different assemblies using indomethacin, ibuprofen and ketoprofen as NSAIDs were easily obtained in water by an acid-base reaction. These assemblies formed new amphiphilic entities because of electrostatic and hydrophobic effects in water and led to the spontaneous formation of vesicles. These catanionic vesicles were then tested as potential NSAID delivery systems for dermatological application. The anti-inflammatory activity was evaluated in vivo, and this study clearly showed an improved therapeutic effect for NSAIDs that were formulated as catanionic vesicles. These vesicles ensured a slower diffusion of the NSAID through the skin. This release probably increased the time of retention of the NSAID in the targeted strata of the skin. Thus, the present study suggests that this catanionic bioactive formulation could be a promising dermal delivery system for NSAIDs in the course of skin inflammation treatment.     

Modulating Properties of Piroxicam,Meloxicam and Oxicam Analogues against Macrophage-Associated Chemokines in Colorectal Cancer

The mechanisms underlying the antineoplastic effects of oxicams have not been fully elucidated. We aimed to assess the effect of classic and novel oxicams on the expression/secretion of macrophage-associated chemokines (RTqPCR/Luminex xMAP) in colorectal adenocarcinoma cells, and on the expression of upstream the non-steroidal anti-inflammatory drug (NSAID)-activated genes NAG1, NFKBIA, MYD88, and RELA, as well as at the chemokine profiling in colorectal tumors. Meloxicam downregulated CCL4 9.9-fold, but otherwise the classic oxicams had a negligible/non-significant effect. Novel analogues with a thiazine ring substituted with arylpiperazine and benzoyl moieties significantly modulated chemokine expression to varying degree, upregulated NAG1 and NFKBIA, and downregulated MYD88. They inhibited CCL3 and CCL4, and their effect on CCL2 and CXCL2 depended on the dose and exposure. The propylene linker between thiazine and piperazine nitrogens and one arylpiperazine fluorine substituent characterized the most effective analogue. Only CCL19 and CXCL2 were not upregulated in tumors, nor was CXCL2 in tumor-adjacent tissue compared to normal mucosa. Compared to adjacent tissue, CCL4 and CXCL2 were upregulated, while CCL2, CCL8, and CCL19 were downregulated in tumors. Tumor CCL2 and CCL7 increased along with advancing T and CCL3, and CCL4 along with the N stage. The introduction of arylpiperazine and benzoyl moieties into the oxicam scaffold yields effective modulators of chemokine expression, which act by upregulating NAG1 and interfering with NF-κB signaling.     

Isocassiaoccidentalin B,A New C‐Glycosyl Flavone Containing a 3‐Keto Sugar,and Other Constituents from Cassia nomame

A new C‐glycosyl flavone containing a 3‐keto sugar, isocassiaoccidentalin B ( 1 ), was isolated from whole Cassia nomame (Sieber ) Honda plants, along with eleven known compounds, including two flavonoids ( 2 and 3 ), five flavonoid glycosides ( 4  –  8 ), two chalcones ( 9 and 10 ), and two phenylpropanoids ( 11 and 12 ). The chemical structures of all compounds were determined via 1D‐ and 2D‐NMR, and ESI‐MS. Among these, compounds 2 , 3 , 7 , and 8 were found to be the most potent in inhibiting nitric oxide release. Compounds 1 , 2 , 4 , 8 , 9 , and 10 showed significant free‐radical scavenging activity.