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Yakugaku Zasshi : Journal of the... 2024Crude drugs and Kampo formulations derived from natural materials such as plants, animals, and minerals are multicomponent medicines that contain numerous chemical... (Review)
Review
Crude drugs and Kampo formulations derived from natural materials such as plants, animals, and minerals are multicomponent medicines that contain numerous chemical constituents. Quantitative determination of characteristic constituents for quality control is crucial for the standardization and quality assurance of natural medicines. Quantitative assays to determine marker compound contents are commonly performed using HPLC systems. In order to achieve accurate quantitative determination, it is essential to use standard materials with well-defined purities corresponding to the target analytes. Many marker compounds used as standard materials must be purified and isolated from natural products while ensuring sufficient purity. However, the composition of impurities in the standard material differs among different batches due to differences in the raw materials and their extraction, separation, and purification processes. Therefore, controlling the purity of standard materials derived from natural products is more complex than that of synthetic substances. Quantitative NMR (qNMR), which has become widely used as an absolute quantitative method for low-molecule organic compounds, makes it possible to solve these issues. qNMR has been introduced into the crude drug section of the Japanese Pharmacopoeia (JP) for evaluating the purity of standard materials used for the assay. This review outlines an example of quantitative determination using relative molar sensitivity (RMS) based on qNMR adopted in the JP and introduces the latest efforts toward the application of qNMR to standard materials used for crude drugs in this context.
Topics: Magnetic Resonance Spectroscopy; Quality Control; Biological Products; Chromatography, High Pressure Liquid; Medicine, Kampo
PubMed: 38556310
DOI: 10.1248/yakushi.23-00151-5 -
Materials (Basel, Switzerland) Aug 2022Silicon nitride (SiN) and silicon powder (Si) are two kinds of harmful solid waste in industrial production. As an environmental and low-consumption method, the...
Silicon nitride (SiN) and silicon powder (Si) are two kinds of harmful solid waste in industrial production. As an environmental and low-consumption method, the cold-bonding technique is a novel method to utilize the problem of powder resource cycling. In this experiment, mechanical and high-temperature properties of Si and SiN briquettes were studied after cold bonding. The results are as follows: (1) The compressive strength of the Si and SiN briquettes increased with the improvement of molding pressure. With the same binder (1 wt.%) and water (10 wt.%) addition, the compressive strength of the SiN briquette arrived at 12,023.53 N under 40 Mpa molding pressure, which is much higher than that of the Si briquette (942.40 N). The Si particles are uneven and irregular, which leads to an intense arch bridge effect in the Si briquette and the compressive strength decrease. Compared with Si powder, the particle size and shape of SiN is small, uniform, and regular. The influence of the arch bridge effect is smaller than that in the Si briquette. (2) After being treated at 1473 K for 1 h, the compressive strength of the Si briquette increased to 5049.83 N, and the compressive strength of the SiN briquette had a slight change. The surface of the briquettes was contacted with oxygen and reacted to form an outer shell which mainly contains SiO in the high-temperature treatment. FT-IR results have shown there were no extra impurities in cold-bonded briquettes when using the organic binder. (3) The microstructure of the cross section of the Si and SiN briquettes after high-temperature treatment presented that oxygen entered the briquette through the pores and continued to react with the Si and SiN. The outer shell of the Si briquette grew and thickened continuously with the oxygen spreading in the Si briquette. However, because of the smaller particle size and regular shape, little oxygen diffused in the SiN briquette. The outer shell of the SiN briquette is fairly thin, so the compressive strength did not change too much.
PubMed: 36013631
DOI: 10.3390/ma15165496 -
Scientific Reports Jul 2021Egg consumption is very high throughout the world and with it comes enormous amount of waste eggshells. To reduce and utilize these wastes, eggshell wastes were simply...
Egg consumption is very high throughout the world and with it comes enormous amount of waste eggshells. To reduce and utilize these wastes, eggshell wastes were simply transformed to low- or high-purity calcium carbonate grades by washing, crushing, and drying to use as raw materials for producing highly valuable calcium phosphate products. Low-purity calcium carbonate grade was used to prepare triple superphosphate for using in fertilizer industry, whereas high-purity calcium carbonate grade was used to produce dicalcium phosphate dihydrate, monocalcium phosphate monohydrate, and tricalcium phosphate for using in mineral feed and food additive industries. All calcium phosphate samples obtained by simple, rapid, cheap, and environmentally safe method using eggshells and phosphoric acid were identified and their structural phases and impurities were determined by XRF, XRD and FTIR techniques. Thermal behaviors of raw materials and the prepared calcium phosphates excepted tricalcium phosphate were investigated by TG/DTG techniques. The methodologies described here will be useful to manage eggshells by converting them to highly valuable products, which can solve eggshell wastes problem from industries and communities. This finding supports the viewpoint of zero waste operation to produce value-added products for obtaining sustainable development, which may be selected as an alternative way for material recycling and waste management in the future.
PubMed: 34312465
DOI: 10.1038/s41598-021-94643-1 -
Materials (Basel, Switzerland) Oct 2021Organic solvents with high purity are essential in various fields such as optical, electronic, pharmaceutical, and chemical areas to prevent low-quality products or...
Organic solvents with high purity are essential in various fields such as optical, electronic, pharmaceutical, and chemical areas to prevent low-quality products or undesired side-products. Constructing methods to remove impurities such as water residue in organic solvents has been a significant challenge. Within this article, we report for the first time a new method for the preparation of hydrophobic and oleophilic filter paper (named OCFP), based on thermally induced silane dehydrocoupling between cellulose-based filter paper and octadecylsilane. We comprehensively characterized OCFP using various characterization techniques (FTIR, XPS, XRD, and EDS). OCFP showed super-hydrophobic and oleophilic properties as well as remarkable water separation and removal efficiency (>93%) in various organic solvents with sustained reusability. In addition, the analytical results both before and after filtration of an NMR solvent using OCFP indicated that OCFP has an excellent solvent drying efficiency. This work presents a new strategy for the development of super-hydrophobic cellulose-based filter paper, which has great potential for solvent drying and water separation.
PubMed: 34640171
DOI: 10.3390/ma14195775 -
Se Pu = Chinese Journal of... Jul 2023Improvements in living standards have led to an increase in the consumption of animal-derived foods. Pesticides may be used illegally during animal breeding as well as...
[High-throughput screening of multi-pesticide residues in animal-derived foods by QuEChERS-online gel permeation chromatography-gas chromatography-tandem mass spectrometry].
Improvements in living standards have led to an increase in the consumption of animal-derived foods. Pesticides may be used illegally during animal breeding as well as meat production and processing for pest control and preservation. Pesticides applied to crops may also be enriched in animal tissues through the food chain, thereby increasing the risk of pesticide residue accumulation in muscles and visceral tissues and endangering human health. China has stipulated maximum residue limits for pesticide residues in livestock and poultry meat and their viscera. Many other major developed countries and organizations, including the European Union, Codex Alimentarius Commission, and Japan, have also set maximum residue limits for these residues (0.005-10, 0.004-10, and 0.001-10 mg/kg, respectively). Research on pretreatment technologies for pesticide residue detection in plant-derived foods is widely available, but insufficient attention has been paid to animal-derived foods. Thus, high-throughput detection technologies for pesticide residues in animal-derived foods are limited. The impurities that can interfere with the detection process for plant-derived foods mainly include organic acids, polar pigments, and other small molecular compounds; by contrast, the matrix of animal-derived foods is much more complex. Macromolecular proteins, fats, small molecular amino acids, organic acids, and phospholipids can interfere with the detection of pesticide residues in animal-derived foods. Thus, selecting the appropriate pretreatment and purification technology is of great importance. In this study, the QuEChERS technique was combined with online gel permeation chromatography-gas chromatography-tandem mass spectrometry (GPC-GC-MS/MS) to determine 196 pesticide residues in animal-derived foods. The samples were extracted with acetonitrile, purified using the QuEChERS technique coupled with online GPC, detected by GC-MS/MS, determined in multiple reaction monitoring mode (MRM), and quantified using the external standard method. The effects of the extraction solvent and purification agent type on the extraction efficiency and matrix removal of the method were optimized. The purification effect of online GPC on the sample solution was investigated. The optimal distillate receiving time was obtained by studying the recoveries of the target substances and matrix effects over different distillate receiving periods to achieve the effective introduction of target substances and efficient matrix removal. Further, the advantages of the QuEChERS technique combined with online GPC were evaluated. The matrix effects of 196 pesticides were assessed; ten pesticide residues showed moderate matrix effects, while four pesticide residues showed strong matrix effects. A matrix-matched standard solution was used for quantification. The 196 pesticides showed good linearity in the range of 0.005-0.2 mg/L, with correlation coefficients greater than 0.996. The limits of detection and quantification were 0.002 and 0.005 mg/kg, respectively. The recoveries of 196 pesticides at spiked levels of 0.01, 0.05, and 0.20 mg/kg were 65.3%-126.2%, with relative standard deviations (RSDs) of 0.7%-5.7%. The proposed method is rapid, accurate, and sensitive; thus, it is suitable for the high-throughput screening and detection of multiple pesticide residues in animal-derived foods.
Topics: Animals; Humans; Pesticide Residues; Tandem Mass Spectrometry; High-Throughput Screening Assays; Gas Chromatography-Mass Spectrometry; Pesticides; Chromatography, Gel
PubMed: 37387282
DOI: 10.3724/SP.J.1123.2022.10010 -
NanoImpact Jul 2022Nanoforms (NFs) of a substance may be distinguished from one another through differences in their physicochemical properties. When registering nanoforms of a substance...
Nanoforms (NFs) of a substance may be distinguished from one another through differences in their physicochemical properties. When registering nanoforms of a substance for assessment under the EU REACH framework, five basic descriptors are required for their identification: composition, surface chemistry, size, specific surface area and shape. To make the risk assessment of similar NFs efficient, a number of grouping frameworks have been proposed, which often require assessment of similarity on individual physicochemical properties as part of the group justification. Similarity assessment requires an understanding of the achievable accuracy of the available methods. It must be demonstrated that measured differences between NFs are greater than the achievable accuracy of the method, to have confidence that the measured differences are indeed real. To estimate the achievable accuracy of a method, we assess the reproducibility of six analytical techniques routinely used to measure these five basic descriptors of nanoforms: inductively coupled plasma mass spectrometry (ICP-MS), Thermogravimetric analysis (TGA), Electrophoretic light scattering (ELS), Brunauer-Emmett-Teller (BET) specific surface area and transmission and scanning electron microscopy (TEM and SEM). Assessment was performed on representative test materials to evaluate the reproducibility of methods on single NFs of substances. The achievable accuracy was defined as the relative standard deviation of reproducibility (RSD) for each method. Well established methods such as ICP-MS quantification of metal impurities, BET measurements of specific surface area, TEM and SEM for size and shape and ELS for surface potential and isoelectric point, all performed well, with low RSD, generally between 5 and 20%, with maximal fold differences usually <1.5 fold between laboratories. Applications of technologies such as TGA for measuring water content and putative organic impurities, additives or surface treatments (through loss on ignition), which have a lower technology readiness level, demonstrated poorer reproducibility, but still within 5-fold differences. The expected achievable accuracy of ICP-MS may be estimated for untested analytes using established relationships between concentration and reproducibility, but this is not yet the case for TGA measurements of loss on ignition or water content. The results here demonstrate an approach to estimate the achievable accuracy of a method that should be employed when interpreting differences between NFs on individual physicochemical properties.
Topics: Metals; Microscopy, Electron, Scanning; Microscopy, Electron, Transmission; Reproducibility of Results; Water
PubMed: 35787478
DOI: 10.1016/j.impact.2022.100410 -
Chemical Science Jun 2023The dark-colored viologen radical cations are unstable in air and easily fade, thus greatly limiting their applications. If a suitable substituent is introduced into the...
The dark-colored viologen radical cations are unstable in air and easily fade, thus greatly limiting their applications. If a suitable substituent is introduced into the structure, it will have the dual function of chromism and luminescence, which will broaden its application field. Here, Vio1·2Cl and Vio2·2Br were synthesized by introducing aromatic acetophenone and naphthophenone substituents into the viologen structure. The keto group (-CHCO-) on the substituents is prone to isomerize into the enol structure (-CH[double bond, length as m-dash]COH-) in organic solvents, especially in DMSO, resulting in a larger conjugated system to stabilize the molecular structure and enhance fluorescence. The time-dependent fluorescence spectrum shows obvious keto-to-enol isomerization-induced fluorescence enhancement. The quantum yield also increased significantly ( = 1 day, = 25.81%, = 41.44%; = 7 days, = 31.48%, and = 54.40%) in DMSO. The NMR and ESI-MS data at different times further confirmed that the fluorescence enhancement was caused by isomerization, and no other fluorescent impurities were produced in solution. DFT calculations show that the enol form is almost coplanar throughout the molecular structure, which is conducive to stabilizing the structure and enhancing fluorescence. The fluorescence emission peaks of the keto and enol structures of Vio1 and Vio2 were at 416-417 nm and 563-582 nm, respectively. The fluorescence relative oscillator strength of Vio1 and Vio2 enol structures is significantly higher than that of keto structures ( value changes from 1.53 to 2.63 for Vio1 and from 1.62 to 2.81 for Vio2), indicating stronger fluorescence emission of the enol structure. The calculated results are in good agreement with the experimental results. Vio1·2Cl and Vio2·2Br are the first examples of isomerization-induced fluorescence enhancement of viologen derivatives, which shows strong solvatofluorochromism under UV light, making up for the disadvantage that it is easy for a viologen radical to fade in air, and providing a new strategy for designing and synthesizing viologen materials with strong fluorescence.
PubMed: 37389262
DOI: 10.1039/d3sc02051g -
Ecotoxicology and Environmental Safety Dec 2021Microplastic pollution represents a global problem with negative impacts on aquatic environment and organisms' health. To date, most of the laboratory toxicological...
Microplastic pollution represents a global problem with negative impacts on aquatic environment and organisms' health. To date, most of the laboratory toxicological studies on microplastics (MPs) have made use of single commercial micro and nano-polymers, which do not reflect the heterogeneity of environmental MPs. To improve the relevance of the hazard assessment, micrometer-sized plastic particles of miscellaneous non-reusable waste plastics, with size <100 µm and <50 µm (waste microplastics, wMPs), were characterized by microscopic and spectroscopic techniques and tested on developing zebrafish and Xenopus laevis by FET and FETAX assays respectively. Moreover, the modalities of wMP interaction with the embryonic structures, as well as the histological lesions, were explored by light and electron microscopy. We have shown that wMPs had very heterogeneous shapes and sizes, were mainly composed of polyethylene and polypropylene and contained metal and organic impurities, as well as submicrometric particle fractions, features that resemble those of environmental occurring MPs. wMPs (0.1-100 mg/L) caused low rate of mortality and altered phenotypes in embryos, but established species-specific biointeractions. In zebrafish, wMPs by adhering to chorion were able to delay hatching in a size and concentration dependent manner. In Xenopus embryos, which open stomodeum earlier than zebrafish, wMPs were accumulated in intestinal tract, where produced mechanical stress and stimulated mucus overproduction, attesting an irritation response. Although wMP biointeractions did not interfere with morphogenesis processes, further studies are needed to understand the underlying mechanisms and long-term impact of these, or even smaller, wMPs.
Topics: Amphibians; Animals; Microplastics; Plastics; Polyethylene; Zebrafish
PubMed: 34536794
DOI: 10.1016/j.ecoenv.2021.112775 -
Se Pu = Chinese Journal of... Apr 2022Siraitia grosvenorii (Swingle) C. Jeffrey, belonging to the family Cucurbitaceae, is a natural sweetener. The roots of this plant are used in folk medicine for the...
Siraitia grosvenorii (Swingle) C. Jeffrey, belonging to the family Cucurbitaceae, is a natural sweetener. The roots of this plant are used in folk medicine for the treatment of rheumatoid arthritis. Cucurbitacins play an important role in the resistance of this plant to insects and adversity, and have anti-inflammatory, anti-tumor, and other biological activities. They usually exist as a variety of similar structures in Cucurbitaceae plants. Separation of a large amount of high-purity monomer compounds by the conventional separation method based on column chromatography is difficult, which limits the research and application of their activities. Therefore, we chose a new method for this separation. High-speed countercurrent chromatography (HSCCC) is a liquid-liquid chromatographic technique characterized by high recovery and reproducibility, and is considered a very effective method for the separation of natural compounds present in various plant extracts. An appropriate solvent system is the key for efficient separation, but its selection is tedious, which hampers the wider implementation of HSCCC in chemical research involving preparative separations. In this study, based on the general estimation strategy by using the TLC solvent system (GUESS), the corresponding relationship between the partition distribution coefficient ( value) and the TLC retention factor ( value) of the compounds was established by the partition experiment. The value and separation coefficient were calculated using the water-saturated organic phase as the expansion agent, which could minimize the number of countercurrent separation experiments required in solvent system selection. In this study, HSCCC was used to establish an efficient method for the extraction of cucurbitacins from the root extract of . A fraction rich in cucurbitacins was obtained from the ethanol extract of roots after separation by column chromatography on HPD-100, MCI, and C18 columns. Six types of solvent systems with different compositions were investigated using the GUESS method. The results showed that employing the solvent system of -hexane-ethyl acetate-methanol-water (3∶7∶3∶7, v/v/v/v) to partition the cucurbitacin fraction could remove a large number of impurities. The components retained in the upper phase in the partition experiment were subsequently purified by HSCCC. The favorable solvent system for HSCCC was -hexane-ethyl acetate-methanol-water (4∶6∶5∶5, v/v/v/v), while the upper and lower phases were selected as the stationary and mobile phases, respectively, with a flow rate of 2.0 mL/min, a rotation speed of 860 r/min, and an injected sample weight of 280 mg. Five cucurbitacin compounds were obtained by one-time separation. The weights of the five compounds were 14.73, 8.82, 30.74, 5.03, and 3.81 mg. The purities of these compounds were 97.0%, 95.4%, 96.3%, 91.6%, and 95.3%, respectively. Their structures were identified as cucurbitacin Q1, 23,24-dihydrocucurbitacin F-25-acetate, cucurbitacin B, 23,24-dihydrocucurbitacin B, and dihydroisocucurbitacin B-25-acetate byH-NMR and C-NMR spectroscopies, along with comparison with the literature. This study demonstrated how GUESS guidance accelerates the selection of HSCCC solvent systems, simplifies the workflow, and it provides an efficient preparative method for the separation of chemical constituents from the roots, which can also be used as a new method for the large-scale preparation of cucurbitacin compounds.
Topics: Countercurrent Distribution; Cucurbitaceae; Cucurbitacins; Reproducibility of Results; Solvents
PubMed: 35362684
DOI: 10.3724/SP.J.1123.2021.07010 -
BMC Chemistry Jan 2024Bromhexine (BR), guaiafenesin (GUF) and salbutamol (SAL) are formulated as Ventocough syrup® (with and without sugar), labeled to contain propyl paraben and sodium...
Bromhexine (BR), guaiafenesin (GUF) and salbutamol (SAL) are formulated as Ventocough syrup® (with and without sugar), labeled to contain propyl paraben and sodium benzoate as inactive ingredients. They are used to make coughing more productive and easier. A crucial element and a major issue in the pharmaceutical industry is the control of organic related impurities to obtain safe and effective treatment. Guaiacol (GUL) is reported to be GUF related impurity that was proved to be extremely toxic (toxic rating class 5), and its use should be banned. In this work, In-Silico study and ADMET estimation were conducted to predict GUL pharmacokinetic properties and its toxicity profile. Additionally, two chromatographic methods were conducted to analyze the studied components along with GUF impurity in the presence of the labeled dosage form excipients. The In-Silico study assured that GUL has oral rat acute toxicity and it is considered to be skin sensitizer. On the other hand, the developed TLC- densitometeric method depended on using a mobile phase mixture of hexane: methylene chloride: triethylamine (5.0:6.0:0.3, by volume) as a developing system. UV-Scanning was performed immediately at 275 nm for SAL, GUF and GUL, while scanning at 310 nm was used for scanning BR. Linearity was established in the ranges of 0.25-4.0, 0.25-4.0, 0.5-8.0 and 0.1-1.6 µg/band for BR, SAL, GUF and GUL, respectively. In the developed HPLC method, separation was performed on X-Bridge® C column (250 × 4.6 mm, 5 μm) using a solvent mixture of 0.05M disodium hydrogen phosphate pH 3 with aqueous phosphoric acid: methanol (containing 0.3%, v/v triethylamine) (40:60, v/v). Detection was done at 225 nm and separation was achieved within 10 min. Linearity was proved in the range of 2-50 µg/mL for the proposed drugs. Validation of the developed methods was done and all the calculated parameters were within the acceptable limits recommended by ICH guidelines. After that, methods were used to examine the potency of the selected marketed dosage forms and concentrations of all drugs were within the acceptable limits. Additionally, complete separation between the studied drugs and the additives were observed. The developed methods can be used during routine quality control analysis of the proposed drugs when the required issues concern on sensitivity, selectivity and analysis time.
PubMed: 38281055
DOI: 10.1186/s13065-024-01122-5