Preparation of COF-coated nickel foam adsorbents for dispersive solid-phase extraction of 16 polycyclic aromatic hydrocarbons from Chinese herbal medicines.

Covalent organic framework coated nickel foam (NF@COF) was prepared as a sorbent for the dispersive solid phase extraction (DSPE) of polycyclic aromatic hydrocarbons (PAHs) from Chinese herbal medicines (CHMs) prior to their determination by gas chromatography-mass spectrometry (GC-MS). The structure and morphology of the as-synthesized NF@COF were characterized by different techniques. Various key parameters affecting the performance of the DSPE method, including the amount of sorbent, desorption solvent, desorption volume and time, extraction time, and sample volume, were investigated. Under the optimized conditions, NF@COF combined with GC-MS was successfully applied to the determination of 16 PAHs in CHMs. The method showed wide linearity (20-2000 ng mL-1), low limits of determination (0.3-2.7 ng mL-1), and high recoveries (78.0-124%). These results revealed that NF@COF has the potential for efficient extraction of PAHs from complex samples.

Determination of polycyclic aromatic hydrocarbons in Chinese herbal medicines by gas chromatography-mass spectrometry with graphene-functionalized nickel foam.

Graphene-functionalized nickel foam (NF) sorbent materials were prepared and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Thermogravimetric analysis. For the separation and detection of polycyclic aromatic hydrocarbons (PAHs) in five Chinese medicine samples, namely dandelion, fructus aurantii, peppermint, mulberry leaf and embryo chrysanthemum, a method combining dispersive micro-solid phase extraction and gas chromatography-mass spectrometry (GC-MS) was developed. Four conditions affecting the extraction efficiency, such as the type of desorption solvent, the amount of sorbent, the extraction time and the volume of water sample, were optimized. The results of the methodological validation showed that NF@SiO2@G was able to adsorb PAHs well and with good reproducibility. All analytes showed good linearity in the concentration range of 20-2000 ng/mL with coefficient of determination R2≥0.9956. The limit of detection was 0.98-13.34 ng/mL, and the limit of quantification ranged from 3.25 to 44.47 ng/mL. Both the intra-day and inter-day precision were lower than 15.46%, and the spiked recoveries were in the range of 75.5-118.4%. The total contents of the 16 PAHs contained in these five Chinese herbal medicines (CHMs) were varied from 450 to 1557 µg/kg. The results indicated that the graphene-functionalized NF sorbent combined with GC-MS can effectively detect PAHs in CHMs.

TIME-Net: Transformer-Integrated Multi-Encoder Network for limited-angle artifact removal in dual-energy CBCT.

Dual-energy cone-beam computed tomography (DE-CBCT) is a promising imaging technique with foreseeable clinical applications. DE-CBCT images acquired with two different spectra can provide material-specific information. Meanwhile, the anatomical consistency and energy-domain correlation result in significant information redundancy, which could be exploited to improve image quality. In this context, this paper develops the Transformer-Integrated Multi-Encoder Network (TIME-Net) for DE-CBCT to remove the limited-angle artifacts. TIME-Net comprises three encoders (image encoder, prior encoder, and transformer encoder), two decoders (low- and high-energy decoders), and one feature fusion module. Three encoders extract various features for image restoration. The feature fusion module compresses these features into more compact shared features and feeds them to the decoders. Two decoders perform differential learning for DE-CBCT images. By design, TIME-Net could obtain high-quality DE-CBCT images using two complementary quarter-scans, holding great potential to reduce radiation dose and shorten the acquisition time. Qualitative and quantitative analyses based on simulated data and real rat data have demonstrated the promising performance of TIME-Net in artifact removal, subtle structure restoration, and reconstruction accuracy preservation. Two clinical applications, virtual non-contrast (VNC) imaging and iodine quantification, have proved the potential utility of the DE-CBCT images provided by TIME-Net.

Molecularly imprinted ratiometric fluorescent probe for visual and fluorescent determination of aristolochic acid I based on a Schiff-base fluorescent compound.

A molecularly imprinted ratiometric fluorescent probe (MIRF probe) was synthesized for the determination of aristolochic acid I (AAI) based on the Schiff-base fluorescent compound N,N'-bis(o-carboxybenzylidene)-p-4,4'-diaminobiphenyl (BDDB). The BDDB was immobilized in the silica nanoparticle (BDDB@SiO2) as an internal standard material. The blue-emitting BDDB@SiO2 and the yellow-emitting carbon quantum dots (y-CDs) were wrapped in the molecularly imprinted polymer (MIP) to provide a reliable reference signal at 440 nm and a fluorescent response signal at 530 nm at the excitation wavelength of 365 nm, respectively. In the preparation of the MIP of the MIRF probe, 4-vinylbenzoic acid as the functional monomer and AAI as the template molecule were used. An imprinting factor of 2.25 was obtained. Under the optimum conditions, the fluorescent response signal at 530 nm was quenched gradually by AAI in the range 1.0 to 120.0 µmol/L, while the reference signal at 440 nm remained unchanged. The limit of detection was 0.45 µmol/L, and the fluorescent color of the MIRF probe changed gradually from yellow to green to blue, which illustrated that the developed probe had a specific AAI recognition ability, a good anti-interference ability, and a sensitively visual determination ability. The probe was successfully applied to the AAI determination in traditional Chinese medicine (TCM) Asarum. The results showed that it had satisfactory recoveries (95.5-107.3%) and low relative standard deviations (2.0%). Furthermore, this method has a potential for the onsite naked eye determination of AAI in TCM samples.Graphical abstract.

A facile one step solvothermal controllable synthesis of FeS2 quantum dots with multiple color emission for the visual detection of aconitine.

Iron disulfide (FeS2) quantum dots have potential applications in various fields such as photocatalysis, lithium-ion batteries and bioimaging. At present, there is no report on the fluorescent characteristics of FeS2 quantum dots (FeS2 QDs). In this work, a synthesis of multiple-color emission FeS2 QDs by changing the temperature, time and raw ratio has been reported. The blue, green, yellow and red emission FeS2 QDs can be obtained, respectively. They were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscope (TEM). On this basis, a novel molecular imprinting ratiometric fluorescence sensor (MIR sensor) had been constructed, in which the blue-emission FeS2 QDs (b-FeS2 QDs) was used as a fluorescent responsive signal material and the yellow-emission FeS2 QDs (y-FeS2 QDs) was served as a reference signal material. And this MIR sensor was applied for highly selective and sensitive detection of ACO in traditional Chinese medicine (TCM). Under the optimum conditions, the MIR sensor exhibited an excellent linear relationship between the fluorescence intensity ratio (I443/I590) and the concentration of ACO in the range of 0.05-5.0 µM with a detection limit of 24 nM. Furthermore, the established method was successfully utilized to the detection of ACO in TCM Fuzi Lizhong Pills with satisfactory results. It provided a reference for the application of the FeS2 QDs with multiple color emission and the detection of the hazardous alkaloids.

Comparative studies on the multi-component pharmacokinetics of Aristolochiae Fructus and honey-fried Aristolochiae Fructus extracts after oral administration in rats.

BACKGROUND: Aristolochiae Fructus (AF) and honey-fried Aristolochiae Fructus (HAF) have been used in China for a long time as anti-tussive and expectorant drugs. Few clinical cases have been reported to be associated with the toxicity of AF and HAF, although relatively high amounts of aristolochic acids (AAs) have been found in them. Our previous experiments have verified from the chemical changes and from traditional toxicology that honey-processing can significantly reduce the toxicity of AF. To further elucidate the detoxification mechanism of honey-processing, comparative pharmacokinetics of AAs in AF and HAF are performed in this study. METHODS: An HPLC-MS/MS (high-performance liquid chromatography-tandem mass spectrometry) method was developed and validated for the determination of AA I, AA II, AA C, AA D and 7-OH AA I in rat plasma. The multi-component pharmacokinetics of AAs in AF and HAF extracts were investigated after the oral administration of three doses to rats. The relative pharmacokinetic parameters were compared systematically. RESULTS: The five AAs shared a similar nonlinear PK (pharmacokinetic) process. They involve rapid absorption and elimination, and they were fit into a two-compartmental open model. Some significant pharmacokinetic differences were observed between the AF and HAF groups: the C max and AUC values of AA I and AA II in the AF groups were much higher than those of the HAF groups. CONCLUSIONS: Honey-frying technology can reduce the toxicity of AF by significantly decreasing the absorption of AA I and AA II. The PK parameters obtained in this work could provide valuable references for the toxicity research and clinical use of Aristolochiaceae herbs, including AF and HAF. Process diagram of comparative pharmacokinetics study.

Component analysis and target cell-based neuroactivity screening of Panax ginseng by ultra-performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry.

Ginseng is one of the most widely used natural medicines in the world. Recent studies have suggested Panax ginseng has a wide range of beneficial effects on aging, central nervous system disorders, and neurodegenerative diseases. However, knowledge about the specific bioactive components of ginseng is still limited. This work aimed to screen for the bioactive components in Panax ginseng that act against neurodegenerative diseases, using the target cell-based bioactivity screening method. Firstly, component analysis of Panax ginseng extracts was performed by UPLC-QTOF-MS, and a total of 54 compounds in white ginseng were characterized and identified according to the retention behaviors, accurate MW, MS characteristics, parent nucleus, aglycones, side chains, and literature data. Then target cell-based bioactivity screening method was developed to predict the candidate compounds in ginseng with SH-SY5Y cells. Four ginsenosides, Rg2, Rh1, Ro, and Rd, were observed to be active. The target cell-based bioactivity screening method coupled with UPLC-QTOF-MS technique has suitable sensitivity and it can be used as a screening tool for low content bioactive constituents in natural products.

Cloud point extraction-HPLC method for the determination and pharmacokinetic study of aristolochic acids in rat plasma after oral administration of Aristolochiae Fructus.

Based on cloud-point extraction (CPE), a high performance liquid chromatography method (HPLC) was developed and validated for the determination of aristolochic acids (AAs) in rat plasma after oral administration of Aristolochiae Fructus (AF). Non-ionic surfactant Genapol X-080, an environmentally friendly solvent, was used for the micelle-mediated extraction. Various influencing factors on CPE process were investigated and optimized. AAs were extracted from rat plasma after adding 1ml of 4.5% (v/v) surfactant in the presence of 0.2mol/l HCl and 20mg NaCl, and the incubation temperature and time were 50°C and 10min, respectively. Base-line separation was obtained for the AAs in rat plasma with the optimized chromatography conditions. The detection limits (LOD) reached downward 10ng/ml. The intra-day and inter-day precisions were less than 7.8%, the accuracies were within ±5.5%, and the average recovery factors were in the range of 94.5-105.4%. In comparison with liquid-liquid extraction, the CPE method has a considerable LOD and higher recoveries. The proposed CPE-HPLC method was specific, sensitive and reliable, and could be an effective tool for the determination of AAs in biological matrixes. With the method the pharmacokinetics of AAs were investigated successfully after oral administration of AF by rats.

[Effect of honey-toasting on the constituents and contents of aristolochic acid analogues in aristolochiae fructus].

OBJECTIVE: To evaluate the degree of de-toxification of Aristolochiae Fructus by honey-toasting technology from chemical viewpoint. METHODS: The contents of aristolochic acid analogues (AAs) in Aristolochiae Fructus and its honey-toasted product were determined by HPLC, and the degree of de-toxification was evaluated comprehensively. RESULTS: After honey-toasted, the contents of AAs decreased to varying degrees, and some new compounds were found. CONCLUSION: The constituents and contents of Aristolochiae Fructus change after honey-toasted, which indicate honey-toasting can reduce the toxicity of Aristolochiae Fructus.

A new strategy based on cholesterol-functionalized iron oxide magnetic nanoparticles for determination of polycyclic aromatic hydrocarbons by high-performance liquid chromatography with cholesterol column.

This study reported for the first time the use of cholesterol-functionalized magnetic nanoparticles (Fe3O4@SiO2@Chol) for the determination of polycyclic aromatic hydrocarbons (PAHs) in traditional Chinese medicine samples (TCMs) by high performance liquid chromatography (HPLC) coupled with fluorescence detection. The method was efficient, environmentally friendly, and fast. The solvent consumption of the proposed column is only half of the conventional column but with higher efficiency. Influencing factors, including sorbent amount, desorption solvent, sample volume and extraction time, were investigated in detail. Under the optimum conditions, good linearity (R(2)>0.991) was obtained over the range of 5-400 ng g(-1), with limits of detection (LOD) 0.75, 0.50, 1.0, 0.56, 0.60, 0.84 and 0.80 ng g(-1) for anthracene, fluoranthene, pyrene, chrysene, benzo[a]anthracene, benzo(b)fluoranthene and benzo(k)fluoranthene, respectively.

Comparative pharmacokinetic studies of peimine and peiminine in rat plasma by LC-MS-MS after oral administration of Fritillaria thunbergii Miq. and Fritillaria thunbergii Miq. - Glycyrrhiza uralensis Fisch. couple extract.

A sensitive LC-MS-MS method has been successfully applied to pharmacokinetic study of peimine and peiminine in rat plasma after oral administration of Fritillaria thunbergii Miq. exact and Fritillaria thunbergii Miq. - Glycyrrhiza uralensis Fisch. couple extract. The results indicated that plasma profiles of peimine and peiminine confirmed to two-compartment open model with weighting function of 1/C2 for data fitting and parameter estimation and the utilization with Glycyrrhiza uralensis Fisch. could decrease C(max) and prolong MRT(0-infinity) and t1/2 of peimine remarkly with the bioavailability of peimine remained practically unchanged. Meanwhile, the concentration of peimine in rat plasma was more stable. Nevertheless, there were no significant differences among all calculated parameters of peiminine.

[Pharmacokinetics of triptolide in Triptergium wilfordii microemulsion gel].

OBJECTIVE: To establish a method of determinating the plasma concentration about the triptolide in rat in vivo. And to study the pharmacokinetics of triptolide in transdermal drug delivery system of Triptergium wilfordii microemulsion gel. METHOD: The T. wilfordii tablet was regarded as the control, the plasma concentration of triptolide was determined by LC-MS/MS after different route of administration, and the pharmacokinetic parameters were calculated by DAS. RESULT: The linear relation of triptolide was excellent within the range of 1-200 ng (r = 0.9967). The minimum detectable concentration were 0.5 microg x L(-1). It was the first-order process. And the pharmacokinetic parameters of triptolide in microemulsion gel was as follow: t(1/2) (2.4 +/- 3.00) h,tmax (6.7 +/- 1.63) h, Cmax (82.9 +/- 17.63) microg x L(-1). To compare the tablets, the microemulsion gel has a longer peak time, and maintain a longer stable plasma concentration. The AUC of tablets and microemulsion gel were (2595.3 +/- 551.15) h x microg x L(-1) and (209.9 +/- 25.34) h x microg x L(-1) and it was a significant differences between the tablet and microemulsion gel (P < 0. 01). CONCLUSION: T. wilfordii has rapid absorption in rat in vivo and a stable and persistent plasma concentration after transdermal drug delivery. Therefore, it is rationality after transdermal drug delivery.

Influence of drug treatment on glucocorticoid receptor levels in patients with coronary heart disease.

BACKGROUND: Glucocorticoid signaling exerts major roles in inflammation, metabolism and depression, which are three crucial factors accompanying or underlying coronary heart disease. Although accumulating evidence indicates the influence of glucocorticoids on the pathology and treatment of coronary heart disease, there is still a dearth of pharmaceutical mechanisms for this relationship. This study aimed to investigate the influence of drug treatment on glucocorticoid receptor levels in coronary heart disease. METHODS: Eighty hospitalized patients (average age (59.0 +/- 7.5) years, 46 male and 34 female) with coronary heart disease were categorized into four groups with 20 members in each according to one of the four drugs they were treated with. The four drugs were: nitrated derivative isosorbide dinitrate, the beta-adrenergic receptor blocker metoprolol, the calcium antagonist nifedipine, and the HMG-CoA reductase inhibitor lovastatin. Glucocorticoid receptor protein levels of peripheral blood lymphocytes were tested using immunoblotting analysis before and after one month of treatment. RESULTS: Immunoblotting analysis showed increased glucocorticoid receptor levels after treatment with metoprolol and nifedipine. There were no statistically significant changes of glucocorticoid receptor levels after treatment with isosorbide dinitrate or lovastatin, although there were trends of up-regulation of glucocorticoid receptor expression after both treatments. CONCLUSIONS: Both the beta-blocker and the calcium blocker can increase glucocorticoid receptor levels after chronic administration. This effect suggests a mechanism for their anti-inflammatory and other therapeutic roles for coronary heart disease and comorbid disorders.

[Preparation and in vitro and in vivo evaluations of topically applied capsaicin transfersomes].

AIM: To prepare capsaicin transfersomes and evaluate them in vitro and in vivo. METHODS: Capsaicin transfersomes were prepared by high shear dispersing machine and evaluated by entrapment efficiency, release rate, in vitro skin permeation and distribution in different tissues in vivo. RESULTS: Capsaicin transfersomes were composed of single unilamellar vesicles with an average diameter of 150.6 nm. Capsaicin entrapment efficiency increased distinctly with increasing of concentration of lecithin and entrapment efficiency is 96.7% while concentration of lecithin to 8%. Cumulative release amount of capsaicin is in direct proportion to the ethanol concentration in the receptor medium. In vitro capsaicin cumulative penetration amount showed higher levels in transfersomes than cream and suspension in rat abdominal skin. Abdominal skin cumulative penetration amount in vitro of capsaicin transfersomes in mouse was significantly higher than that from rat and men. In the same way, abdominal skin epidermal membrane cumulative penetration amount in vitro of capsaicin transfersomes was significantly higher than that from derma and full skin in human abdominal skin. The capsaicin tissue distribution of capsaicin injection by multiple celiac injections in rats is different: bone > plasma > skin > muscle. There is a similar result by multiple thigh topical application of capsaicin transfersomes: bone > skin > plasma > muscle. CONCLUSION: Entrapment efficiency of capsaicin transfersomes reached the criterion of China Pharmacopoeia (> 80%) and capsaicin skin penetration can be increased by capsaicin transfersomes. It should be noted that the diverse characters and levels of skin may probably affect the permeating capability of capsaicin. Capsaicin tissue distribution in bone and muscle is similar and is different in plasma and skin by multiple injections and topical skin apply.