To achieve rapid and non-destructive identification of safflower seeds, a qualitative identification model was constructed based on near-infrared spectroscopy (NIRS) combined with chemometric methods including principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA), backpropagation neural networks (BPNN), and convolutional neural network (CNN). Results: The model utilizing raw safflower seed spectra combined with BPNN demonstrated the highest performance in variety differentiation, achieving 100% prediction accuracy on both the training and test sets. The model combining raw spectra with CNN ranked second, with prediction accuracies of 100% and 97.235% respectively. The synergistic integration of neural networks' deep learning prowess with the inherent benefits of near-infrared spectroscopy establishes a robust analytical framework for safflower seed germplasm authentication. This methodology presents substantial potential as an advanced approach for provenance verification and quality surveillance in both food and pharmaceutical sectors.

Objective: Near Infrared Spectroscopy (NIRS) combined with chemometrics were used to establish the discriminant model of Dendrobium huoshanense under different cultivation modes so as to realize the rapid identification of the Dendrobium huoshanense under different cultivation modes. Methods: A portable near-infrared spectrometer was used to determine the near-infrared spectra of 152 Dendrobium huoshanense fengdou samples collected from three cultivation modes (facility cultivation, under forest cultivation, and simulative habitat cultivation). Raw spectral data were preprocessed using Standard Normal Variation (SNV), SavitzkyGolay (SG), and Competitive Adaptive Reweighed Sampling (CARS), either individually or in combination. Then, a data model based on Partial Least Squares Discriminant Analysis (PLS-DA) was established and the effects of different spectral preprocessing methods on the accuracy of the PLS-DA model were also compared. Results: The preprocessing method of SNV was more effective, under the potential variable of 10, and the PLS-DA calibration model could predict Dendrobium huoshanense under the three cultivation modes according to their spectral information with the prediction accuracy of >91.2%. Conclusions: The quantitative model of Dendrobium huoshanense established by using NIRS is stable and reliable, which can realize the rapid identification of the quality of Dendrobium huoshanense in the market, and provides a new method for the rapid and nondestructive identification of Dendrobium huoshanense.

An improved black-winged kite algorithm with multiple strategies (BKAIM) is proposed in this paper to address two critical limitations in the original black-winged kite optimization algorithm (BKA): the restricted search capability caused by the low-quality initial population and the reduced population diversity resulting from blind following behavior during the migration phase. Our enhancement implements three strategic modifications across different algorithm stages. During initialization, an opposition-based learning strategy was incorporated to generate a higher-quality initial population. For the migration phase, a differential mutation strategy was integrated to facilitate information exchange among population members, mitigate the tendency of blind leader-following behavior, enhance convergence precision, and achieve an optimal balance between exploration and exploitation capabilities. Regarding boundary handling, the conventional absorption boundary method was replaced with a random boundary approach to increase population diversity and subsequently improve the algorithm’s search capabilities. Comprehensive testing was conducted on four benchmark function sets (CEC2017, CEC2019, CEC2021, and CEC2022) to validate the effectiveness of the improved algorithm. Detailed convergence analysis and Wilcoxon rank-sum test comparisons with other algorithms demonstrated BKAIM’s superior convergence performance and robustness. Furthermore, the support vector machine (SVM) model was optimized by BKAIM for grade identification of Dendrobium huoshanense based on near-infrared spectral data, thereby confirming its effectiveness in practical applications.

Microbial glycosyltransferases efficiently synthesize glucosides and have garnered increasing interest. However, limited regioselectivity has impeded their broad application, particularly in the pharmaceutical industry. In this study, the UDP-glycosyltransferase YjiC from Bacillus licheniformis (BlYjiC) was engineered to achieve the bidirectional regioselective glycosylation of tyrosol and its derivatives. Initially, site-directed saturation mutagenesis was performed on two newly identified substrate-binding cavities in the acceptor pocket of BlYjiC to provide a comprehensive blueprint of the interplay between mutations and function (mutability landscape). Iterative saturation mutagenesis was performed, guided by the mutability landscape. Two highly regioselective mutants M6 (M112L/I325Y/L70R/Q136E/I67E/M77R) and M2' (M112D/I62L) were generated, exhibiting >99 % regioselectivity toward the alcoholic and phenolic hydroxyl of tyrosol, respectively, compared with the wild -type (product mixture: 51:49 %). Both mutants exhibited excellent regioselectivity toward several dihydroxy phenolic substrates, offering valuable biocatalysts for the regioselective synthesis of glucosides. Their application was confirmed in a short synthesis of salidroside (3.6 g/L) and icariside D2 (2.4 g/L), which exhibited near-perfect regioselectivity. This study provides valuable insights into future protein engineering of similar enzymes and opens new avenues for their practical applications.

Poor stability and difficult uptake of natural polysaccharides have been the main problems in their application. The purpose of this study was to optimize the preparation conditions of Polygonatum cyrtonema Hua polysaccharides liposomes (PCPL) and to investigate the immune enhancement activity of PCPL in vitro and in vivo, with a view to discovering new ways of natural polysaccharide application. The optimal preparation conditions of PCPL were as follows: the adding amount of Tween 80 of 0.5 %, the ultrasound time of 2 min and the ultrasound times of once. Under these conditions, the entrapment efficiency, drug loading rate and particle size of PCPL were 38.033 %±0.050, 2.172 %±0.003 and 146 nm, which indicated that PCPL with small particle size could be prepared by the reverse-phase evaporation method. Furthermore, PCPL promoted proliferation, phagocytosis, and secretion of nitric oxide and related cytokines in RAW264.7 cells. Moreover, PCPL improved spleen and thymus indices, increased the number or proportion of red blood cells, platelets, and lymphocytes in the blood, and ameliorated spleen and thymus atrophy in immunosuppressed mice. This study provides a new idea for applying Polygonatum cyrtonema Hua polysaccharides (PCP) and references for studying other polysaccharides.

The confusing use of Polygonati Rhizoma (PR) and Polygonati Odorati Rhizoma (POR) poses an unpredictable threat to the health of consumers. Sensitive, nondestructive, rapid, and multicomponent techniques for their detection are sought after. In this study, a low-cost, short-wavelength (898–1668 nm), and handheld near-infrared (NIR) spectrometer combined with multivariate spectral evaluation methods was used to establish calibration models for identifying PR and POR. NIR spectra were treated with a standard normal variate (SNV) before performing chemometric approaches. Then principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were tested for calibration model development. The PCA results showed that spectral differences existed between the two herbs. However, the evaluation techniques could not separate them with the required accuracy. The PLS-DA calibration model, on the other hand, could separate the two herbs according to their spectral information with the prediction accuracy of >98.3%. Thus, it has been proven that a rapid, green, and low-cost method to support on-site and practical inspection through a handheld NIR instrument has been established to identify PR and POR and ensure the safety of the clinical medication.

The branch waste of sweet cherry trees is an organic byproduct that is inevitably produced during the pruning process. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used to analyze and compare the differences in the chemical composition and the presence of macroelements in the xylem and bark of sweet cherry branches. The FTIR absorption spectra were analyzed, and the following absorption peaks were found: 1632 cm-1 for lignin, 1740 cm-1 and 1244 cm-1 for hemicellulose, and 1316 cm-1 for holocellulose. The results showed that the lignin content in the bark was higher than that in the xylem, and the content of hemicellulose and holocellulose in the xylem was higher than that in the bark. The XPS survey showed that the sweet cherry branches were mainly composed of C and O, with binding energies of approximately 285 eV and 532 eV, respectively. The contents of C-C (9.89% and 15.59%, respectively) and C=O (31.52% and 15.59%, respectively) in xylem and bark were quite different; the xylem had a higher cellulose content, while the bark had a higher lignin content. In the xylem, the proportion of C-O was the largest (12.55%) and the proportion of O=C-O was the second largest (12.51%), while in the bark, the proportion of C=O was the highest (5.93%), and the proportion of O=C-O was the second highest (4.48%). The N contents in xylem and bark were 2.5% and 5.75%, respectively. The S content was very low. The research results are significant for revealing the chemical composition and structural morphology of the xylem and bark of sweet cherry branches.

Acacia catechu (L.f.) Willd, a leguminous plant, is included in the 2020 edition of the Chinese Pharmacopoeia and is mainly used to treat eczema, mouth ulcers, diarrhea, bruising, and traumatic hemorrhage. However, there are imported and domestic Acacia catechu samples available in China, and their quality and price are very different, which seriously affects the safety and stability of their clinical application. Importantly, there is no simple and effective method for identifying or classifying grades of Acacia catechu. In this study, 47 batches of commercial Acacia catechu were used for identifying or classifying grades of Acacia catechu using high performance liquid chromatography (HPLC) combined with chemometric analysis. Firstly, gradient elution was adopted with 0.05% phosphoric acid water (A)-methanol (B) as the mobile phase to establish chromatographic conditions. The HPLC chromatograms of 47 batches of Acacia catechu samples were analyzed by the “Similarity Evaluation System for Chromatographic Fingerprint of TCM” software (version 2012A). The common peaks of Acacia catechu were identified to evaluate the similarity. Based on the determination results of fingerprint chromatographic peak area, the quality of the collected Acacia catechu was evaluated by chemometric methods such as CA, PCA, and OPLS-DA. The results showed that the collected Acacia catechu samples were significantly divided into three categories. The first-class samples were all imported Acacia catechu except S9 sample, which was domestic Acacia catechu; the second-class samples were partly domestic Acacia catechu and partly imported Acacia catechu; and the third-class samples were all domestic Acacia catechu. Moreover, OPLS-DA of 47 batches of samples showed that the contents of catechin and the total contents of catechin and epicatechin could be used as key indicators for assessing the quality of Acacia catechu. The developed HPLC fingerprint and quantitative analysis method of multi-indicator components can be used for classification and quality evaluation of market Acacia catechu, which has a significant reference value for developing Acacia catechu grade quality standards.

Docetaxel (DTX) is an important broad-spectrum antitumor drug, but poor water solubility and multidrug resistance often limit clinical application. A nitric oxide (NO) donor docetaxel prodrug (DISMN-DTX) was designed and synthesized, through a two-step procedure starting from isosorbide mononitrate. The novel amphiphilic small molecule prodrug is readily self-assembled into nanoplatforms, which effectively solves the significant obstacle of poor water solubility of DTX. Specifically, the DISMN-DTX nanoplatforms could trigger NO release at the intracellular reduction conditions to improve the chemosensitivity of DTX. Thus, our rationally designed prodrug nanoplatforms provide an efficient treatment option for drug-resistant tumors.

Thrombosis, which seriously endangers human health and life, is the leading cause of morbidity and mortality globally. Antithrombotic drugs can interfere with the occurrence and development of thrombotic diseases and play an important role in the treatment of thrombotic diseases. However, unsatisfactory efficacy and serious adverse effects of existing antithrombotic drugs increase the research for new, efficient and safer drugs. Natural and synthetic coumarins have been shown to possess antithrombotic activity, namely, anticoagulation and antiplatelet aggregation. Especially, coumarin-based warfarin, phenprocoumon and cloricromen have long been used in clinical treatment of thrombosis. Coumarin with low toxicity is the privileged structure for developing novel antithrombotic drugs with multiple mechanisms of action. The present review aims to compile current research on the development of coumarins against thrombosis, emphasizing the relationship between their chemical structures and therapeutic effectiveness. It is intended to provide promising ideas for the discovery of novel coumarin derivatives with high antithrombotic activity.

目的 分析15种市售坚果中氨基酸组成,比较不同品种坚果间必需氨基酸、非必需氨基酸含量的差异.方法 使用氨基酸分析仪对样品中氨基酸的组成及含量进行分析,用最小显著性差异法(least-significant difference,LSD)进行多重比较.结果 纸皮核桃中的必需氨基酸含量最高,为6.264 g/100 g,花生中总氨基酸含量最高,为22.622 g/100 g.使用模糊辨识法对贴近度进行计算得出,FAO/WHO模式蛋白质贴近度为0.840～0.933.结论 坚果中必需氨基酸和总氨基酸含量的差异显著.限制氨基酸均为蛋氨酸和胱氨酸.东北松子的FAO/WHO模式蛋白质贴近度最高,最贴近人体所需蛋白质的模式.

目的 使用异硫氰酸苯酯衍生-高效液相色谱法对食品中17种游离氨基酸进行检测.方法 对17种游离氨基酸及其苯胺硫甲酰基衍生物稳定性的分析,研究游离氨基酸的最佳衍生条件.同时,对盐沉淀法和C18固相萃取(solid phase extraction,SPE)小柱法2种样品除杂方法 的加标回收率进行测定.结果 胱氨酸加热干燥5 h后,回收率为68.46％±4.01％,热稳定性差;其它16种氨基酸加热1～5 h后回收率均在90％～110％之间,热稳定性较好.胱氨酸的苯胺硫甲酰基衍生物,6 h后回收率仅为11.04％±1.65％,稳定性差;其它氨基酸的苯胺硫甲酰基衍生物24 h后回收率均大于90％,比较稳定.另外,前处理中使用C18 SPE除杂时,样品中游离氨基酸的加标回收率均大于70％,而使用水杨酸和三氯乙酸除蛋白后苯胺硫甲酰基衍生物降解严重.结论 除胱氨酸外,其余16种氨基酸的热稳定性均较好,且生成的苯胺硫甲酰基衍生物比较稳定,可以通过异硫氰酸苯酯衍生进行定量分析.相比于水杨酸和三氯乙酸沉淀法,C18 SPE柱是游离氨基酸除杂方法 的首选,而无机盐影响异硫氰酸苯酯与氨基酸衍生,因此此方法 不适用于含盐样品的衍生.

目的 采用响应面法和正交实验法对天山岩黄芪中多酚的提取及分离纯化工艺进行优化.方法 采用单因素和响应面法确定天山岩黄芪多酚提取最佳工艺;筛选最佳型号的大孔吸附树脂,利用正交实验法优化大孔吸附树脂对天山岩黄芪多酚纯化分离的工艺.结果 天山岩黄芪多酚提取的最佳工艺参数为:提取所用乙醇浓度为60％(V/V),料液比为1∶25(m/V),提取温度为60℃提取时间为1.5 h.采用此方法提取天山岩黄芪多酚的含量为0.3316 mg/g;对天山岩黄芪多酚纯化的最佳大孔吸附树脂型号为HPD 500(径高比为1∶5),最佳工艺参数为:上样量0.3柱床体积(bed volume,BV,1 BV=90 mL),65％乙醇洗脱,上样浓度为9％,此方法纯化天山岩黄芪多酚,含量为40.94 mg/g.结论 采用响应面法实验优化法提取天山岩黄芪多酚,工艺稳定可靠;HPD500型大孔吸附树脂对天山岩黄芪多酚类物质纯化效果良好,可为天山岩黄芪中多酚的制备工艺提供参考.

A simple, accurate and sensitive method of high performance liquid chromatography (HPLC) with diode array detector was established to identify Xinfeng capsules and systematically evaluated its quality, based on chromatographic fingerprint integrated with the similarity analysis, hierarchical cluster analysis and the quantitative analysis of multi-components by single marker (QAMS). In this study, 18 peaks were selected as the common peaks to evaluate the similarities among different batches (S1-S10) of Xinfeng capsules samples, which were manufactured in the First Affiliated Hospital of Anhui University of Chinese Medicine with a three-year span. Compared to control fingerprint, the similarities values for 10 batches of samples were more than 0.90. Moreover, by analyzing the reference of astragalus, the chromatogram of astragalus was developed, and 10 common peaks of astragalus were identified. More importantly, simultaneous quantification of three markers in Xinfeng capsule, including Calycosin-7-glucoside, calycosin and Formononetinaldehyde was performed, the three constituents showed good regression (R > 0.999) within linear ranges, and their recoveries were within the range of 97.6-101.5%. The validation results showed that the developed method was specific, accurate, precise and robust. This study demonstrated that the developed method offers an efficient, reliable and practical approach for systematic quality evaluation of Xinfeng capsule.

A novel magnetic nanocomposite was prepared and applied for the extraction of organophosphorus pesticide residue (malathion, chlorpyrifos, isocarbophos, fenamiphos, profenofos) in environmental water by magnetic solid phase extraction. The magnetic nanocomposite was synthesized by coating Fe3O4 with silicon dioxide and then bonding with graphene oxide under the catalytic action of hydrazine hydrate. A residue analysis method for the determination of organophosphorus pesticides in environmental water was established via magnetic solid phase extraction with the nanocomposite as the sorbent, followed by gas chromatography with flame photometric detection (GC-FPD). Various experimental parameters affect extraction efficiency and must be optimized, such as the sorbent amount, the type and volume of desorption solvent, desorption time, desorption step, salt concentration and pH. Under the optimum conditions, a linear response was achieved for malathion and chlorpyrifos in the concentration range of 0.05 mg L-1-5 mg L-1. Other organophosphorus pesticides were quantified in a concentration range of 0.1 mg L-1-5 mg L-1, and the coefficient of correlations were between 0.996 and 1 for this method. The method was used to determine organophosphorus pesticides in river water and groundwater. The average recoveries ranged from 90.2% to 102.9%, with low relative standard deviations (RSD), and the limits of detection (LOD) were between 0.016 mg L-1 to 0.033 mg L-1 at a signal to noise ratio of 3. The method was efficient for the residue analysis of organophosphorus pesticides in water with easy operation, high sensitivity, and good precision.

Pesticides are frequently detected in water bodies due to the agricultural application, which may pose impacts on aquatic organisms. The enantioselective bioaccumulation and metabolism of the herbicide lactofen in aquatic floating macrophyte Lemna minor (L. minor) were studied and the potential L. minor phytoremediation was investigated. Ultra-high performance liquid chromatography – tandem mass spectrometry (UHPLC-MS-MS) analysis for lactofen and its two known metabolites in L. minor was performed. The initial concentrations of racemic lactofen, R-lactofen and S-lactofen were all 30 μg L−1 in the growth solution. The distribution of lactofen and its metabolites in growth solution and L. minor was determined throughout a 5-d laboratory trial. It was observed that S-lactofen was preferentially taken up and metabolized in L. minor. After rac-lactofen exposure, the accumulation amount of S-lactofen was approximately 3-fold more than that of R-lactofen in L. minor and the metabolism rate of S-lactofen (T1/2=0.92 d) was significantly faster than R-lactofen (T1/2=1.55 d). L. minor could only slightly accelerate the metabolism and removal of lactofen in the growth solution. As for the metabolites, desethyl lactofen was found to be the major metabolite in L. minor and the growth solution, whereas the metabolite acifluorfene was undetectable. No interconversion of the two enantiomers was observed after individual enantiomer exposure, indicating they were configurationally stable. The findings of this work represented that the accumulation and metabolism of lactofen in L. minor were enantioselective, and L. minor had limited capacity for the removal of lactofen and its metabolite in water.

Pesticides have long been considered to a risk factor of amphibian population declines. The bioaccumulation and elimination of fenoxaprop-ethyl (FE) in frogs and tadpoles were studied and the main metabolites fenoxaprop (FA) and 6-chloro-2,3-dihydrobenzoxazol-2-one (CDHB) were monitored. The acute toxicity and genotoxicity of the enantiomers to tadpoles was also studied. After both oral administration and aqueous solution exposure, FE was not found in frogs, while FA was formed and accumulated in liver, kidney, brain, eggs, skin, thigh muscle and blood with preferential accumulation of R-FA. The presence of FA in frog eggs suggested maternal transfer in females and potential impacts to offsprings. The elimination of FA in frog tissues was also enantioselective with a preferential metabolism of R-FA (kidney) or S-FA (liver, eggs, skin, muscle and whole blood). FE and FA were hardly detectable in tadpoles after aqueous solution exposure, while CDHB was accumulated and eliminated as first-order kinetics with half-life of 37.1 h. Mortality of tadpoles and micronucleus rate in peripheral blood erythrocytes of tadpoles were used to evaluate the enantioselective acute toxicity and genotoxicity. Only CDHB induced significant acute toxicity to tadpole with 96-h LC50 value of 30.4 μg/mL, and rac-FA, S-FA and CDHB showed genotoxicity.

The enantioselective bioaccumulation and elimination of fipronil in Anodonta woodiana (A. woodiana) were studied and the main metabolites fipronil desulfinyl, fipronil sulfide and fipronil sulfone were determined. The acute toxicity of the enantiomers of fipronil and the three metabolites were also investigated. In the bioaccumulation process, fipronil in A. woodiana reached equilibrium after 11days with BCF value of 0.2, and the enantiomeric fraction (EF) values showed that the bioaccumulation was enantioselective with enantioenrichment of S-fipronil. The degradation of fipronil in A. woodiana fitted first-order kinetics model with half-lives of the enantiomers were 5.8 d for R-fipronil and 7.6 d for S-fipronil, and the EF values decreasing from 0.5 gradually indicating the R-enantiomer was preferentially degraded. The degradation of single enantiomers was also performed and the results revealed a fast conversion of R-fipronil to S-fipronil by A. woodiana. The three metabolites were all detected in A. woodiana-water system, in which fipronil sulfone and fipronil sulfide had higher concentration levels. According to the 72-h LC50 values, S-fipronil was much more toxic than the racemate and R-fipronil. Moreover, the metabolites were more toxic than the parent fipronil. The results suggested the individual enantiomers of chiral pollutants and the metabolites should be considered in the risk assessments.

Pesticide pollution of surface water represents a considerable danger for the aquatic plants which play very crucial roles in aquatic system such as oxygen production, nutrient cycling, water quality controlling and sediment stabilization. In this work, the toxic effects of the chiral herbicide lactofen and its three metabolites (desethyl lactofen, acifluorfene and amino acifluorfene) to the aquatic plant Lemna minor (L. minor) on enantiomeric level were evaluated. The influences on growth rate, fresh weight, content of photosynthetic pigment, protein and malondialdehyde (MDA) and the activities of antioxidant defense enzymes (catalase (CAT) and superoxide dismutase (SOD)) were measured after 7 days of exposure. L. minor growth was inhibited in the order of (S)-desethyl lactofen > racemic-desethyl lactofen > (R)-desethyl lactofen > racemic-lactofen > (S)-lactofen > (R)-lactofen > acifluorfene > amino acifluorfene, and the IC50 (7d) values showed desethyl lactofen was the most powerful compound which was about twice as toxic as lactofen. The contents of chlorophylls (Chl) and carotenoids (Car) were significantly reduced by the chemicals, while, the levels of protein, MDA and the activity of CAT and SOD enzymes increased in most cases. The obtained results revealed that lactofen and its metabolites had an undesirable effect on L. minor, in terms of physiological and biochemical aspects. Besides, enantioselective toxicity of lactofen and desethyl lactofen to L. minor was observed. The S-enantiomer of desethyl lactofen was more toxic than the corresponding R-enantiomer. Furthermore, racemic lactofen was more toxic than the individual enantiomers. The side effects of pesticide metabolites and the enantioselectivity should be considered in developing optically pure products and risk assessment.