Phytonutrients,Colorant Pigments,Phytochemicals, and Antioxidant Potential of Orphan Leafy Amaranthus Species

The underutilized Amaranthus leafy vegetables are a unique basis of pigments such as β-cyanins, β-xanthins, and betalains with radical scavenging capacity (RSC). They have abundant phytonutrients and antioxidant components, such as pigments, vitamins, phenolics, and flavonoids. Eight selected genotypes (four genotypes from each species) of underutilized Amaranthus leafy vegetables were evaluated for phytonutrients, pigments, vitamins, phenolics, flavonoids, and antioxidants in a randomized complete block design under ambient field conditions with three replicates. The studied traits showed a wide range of variations across eight genotypes of two species of Amaranthus leafy vegetables. The highest fat, β-xanthins, K, dietary fiber, Mg, β-cyanins, Mn, chlorophyll ab, Zn, TP, TF, betalains, chlorophyll a content, and (RSC) (DPPH) and RSC (ABTS⁺) were obtained from A. tricolor accessions. Conversely, the highest protein, Cu, carbohydrates, Ca, and chlorophyll b content were obtained from A. lividus accessions. The highest dry matter, carotenoids, Fe, energy, and ash were obtained from A. tricolor and A. lividus. The accession AT2 confirmed the highest vit. C and RSC (DPPH) and RSC (ABTS+); AT5 had the highest TP content; and AT12 had the highest TF content. A. tricolor accessions had high phytochemicals across the two species, such as phytopigments, vitamins, phenolics, antioxidants, and flavonoids, with considerable nutrients and protein. Hence, A. tricolor accessions can be used as high-yielding cultivars comprising ample antioxidants. The correlation study revealed that vitamin C, pigments, flavonoids, β-carotene, and phenolics demonstrated a strong RSC, and showed a substantial contribution to the antioxidant potential (AP) of A. tricolor. The investigation exposed that the accessions displayed a plentiful origin of nutritional values, phytochemicals, and AP with good quenching ability of reactive oxygen species (ROS) that provide enormous prospects for nourishing the mineral-, antioxidant-, and vitamin-threatened community.     

Selective Differential Spectrophotometric Methods for Determination of Niclosamide and Drotaverine Hydrochloride

ABSTRACT

Differential (ΔA), second derivative (ΔD²) and third derivative (ΔD³) differential ultraviolet spectrophotometric methods have been presented for the quantitation of niclosamide and drotaverine hydrochloride in pure forms and in their pharmaceutical formulations. For niclosamide, the method is based on measuring ΔΔ A, Δ ΔD², A ΔD³ of niclosamide in alkaline solutions against their neutral ethanolic solutions as blanks. For drotaverine hydrochloride, the acidic solutions of the drug are measured against their alkaline solutions as blanks. The proposed methods are sensitive, highly specific and advangageous over the conventional UV assays, since the interference of the excipients, impurities, degradation products or other accompanying drugs is nullified. Accuracy of the analysis with the proposed procedures is significantly greater than the classical spectrophotometric methods.     

Simple DPPH.‐Based Electrochemical Assay for the Evaluation of the Antioxidant Capacity: a Thorough Comparison with Spectrophotometric Assays and Evaluation with Real‐World Samples

An assay based on the electrochemical detection of 2,2‐diphenyl‐1‐picrylhydrazyl radical (DPPH^.) for the evaluation of the total antioxidant capacity (TAC) was optimized. The assay is interchangeable with the classic spectrophotometric tests for TAC based on the same radical. In addition, it can be used for the analysis of dilute samples with low antioxidant capacities. A good linear correlation (R²=0.97) was obtained between the results obtained with the proposed electrochemical assay and the Trolox Equivalent Antioxidant Capacity test based on ABTS radical. The assay was successfully used to evaluate the antioxidant capacity of two red wines obtained by six different maceration‐fermentation techniques.     

Antioxidant Extracts of Nettle (Urtica dioica) Leaves: Evaluation of Extraction Techniques and Solvents

Nettle (Urtica dioica) is a great source of bioactive compounds. The objective of this study was to evaluate the extraction techniques (ultrasound, without stirring, and stirring), solvents (methanol, water, and ethanol), and extraction times (1–4 h) to maximize antioxidant capacity of the Urtica dioica extracts. In the case of total phenolic content (TPC) and ABTS^•+ (2,2-azino-bis(3-etilbenzotiazolin)-6-sulfonic acid) free radical scavenging values, ultrasound extraction was the most efficient method, while the best results of DPPH^• (1,1-diphenyl-2-picrylhydrazyl) assay in nettle extracts (91.08%) were obtained using stirring extraction, water as solvent, and 3 h of extraction time. Based on the obtained mathematical models, the optimization revealed that the best extraction conditions were ultrasound treatment with water as solvent and an extraction time of 3.15 h, obtaining values of 21.9 mg eq gallic acid/g dried nettle for TPC, 71.8% for %ABTS^•+ and 86.6% for %DPPH^•. This work proves that aqueous extract of nettle leaves through the ultrasound technique is an important source of natural antioxidants and can be considered a potential alternative to synthetic antioxidants.     

Analytical Methods for the Determination of 90Sr and 239,240Pu in Environmental Samples

Artificial long-lived radionuclides such as ⁹⁰Sr and ^239,240Pu have been long released into the environment by human nuclear activities, which have a profound impact on the ecological environment. It is of great significance to monitor the concentration of these radionuclides for environmental safety. This paper summarizes and critically discusses the separation and measurement methods for ultra-trace determination of ⁹⁰Sr, ²³⁹Pu, and ²⁴⁰Pu in the environment. After selecting the measurement method, it is necessary to consider the decontamination of the interference from matrix elements and the key elements, and this involves the choice of the separation method. Measurement methods include both radiometric methods and non-radiometric methods. Radiometric methods, including alpha spectroscopy, liquid scintillation spectrometry, etc., are commonly used methods for measuring ^239+240Pu and ⁹⁰Sr. Mass spectrometry, as the representative of non-radiometric measurement methods, has been regarded as the most promising analytical method due to its high absolute sensitivity, low detection limit, and relatively short sample-analysis time. Through the comparison of various measurement methods, the future development trend of radionuclide measurement is prospected in this review. The fully automatic and rapid analysis method is a highlight. The new mass spectrometer with ultra-high sensitivity shows strong analytical capabilities for extremely low concentrations of ⁹⁰Sr, ²³⁹Pu, and ²⁴⁰Pu, and it is expected to develop determination methods with higher sensitivity and lower detection limit.     

Comparison of Partial Least Squares Regression and H-Point Standard Addition Method for Simultaneous Spectrophotometric Determination of Zinc, Cobalt and Nickel by 1-(2-Pyridylazo)2-Naphthol in Micellar Media

Simultaneous spectrophotometric methods are described for the determination of Zn²⁺, Co²⁺ and Ni²⁺ by 1-(2-pyridylazo)2-naphthol (PAN) in micellar media, using absorbance correction-H-point standard addition method (HPSAM) and partial least squares (PLS) regression. The ligand and its metal complexes, i.e. Zn²⁺-PAN, Co²⁺-PAN and Ni²⁺-PAN, were made water-soluble by the neutral surfactant Triton X-100, and therefore extraction with organic solvents was no longer required. Formation of all of these complexes was complete within 10min at pH 9.2. The linear range was 0.1–1.5mgL^–1 for Zn²⁺, 0.1–2.0mgL^–1 for Co²⁺ and 0.1–2.0mgL^–1 for Ni²⁺. The relative standard deviation (RSD) for the simultaneous determination of 0.50mgL^–1 each of Zn²⁺, Ni²⁺ and Co²⁺ by applying the H-point standard addition method was 2.55%, 2.04% and 3.70%, respectively. The total relative standard error for applying the PLS method to 9 synthetic samples in the linear ranges of these metals was 1.8%. Interference effects of common anions and cations were studied, and both methods were applied to the simultaneous determination of Zn²⁺, Co²⁺ and Ni²⁺ in alloy samples.     

Classification of Wines Based on Combination of ^1H NMR Spectroscopy and Principal Component Analysis

A combination of ^1H nuclear magnetic resonance （NMR） spectroscopy and principal component analysis （PCA） has shown the potential for being a useful method for classification of type, production origin or geographic origin of wines. In this preliminary study, twenty-one bottled wines were classified/separated for their location of production in Shacheng, Changli and Yantai, and the types of the blended, medium dry, dry white and dry red wines, using the NMR-PCA method. The wines were produced by three subsidiary companies of an enterprise according to the same national standard. The separation was believed to be mainly due to the fermentation process for different wines and environmental variations, such as local climate, soil, underground water, sunlight and rainfall. The major chemicals associated with the separation were identified.     

The antioxidant activity of wines determined by the ABTS(+) method: influence of sample dilution and time

The free radical scavenging activity of 42 Spanish commercial wines was determined using the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation (ABTS⁺). The ABTS⁺ radical was generated enzymatically using a horseradish peroxidase and hydrogen peroxide. The presence of wine phenolic compounds caused the absorbance of the radical to decay at 414 nm. The measurement conditions were optimised. The total phenolic content of wines ranged from 1262 to 2389 mg l⁻¹ for red wines and 70 to 407 mg l⁻¹ for white wines, expressed as gallic acid equivalents. The phenolic content of Sherry wines was similar to that of white wines. Optimum dilutions for white and Sherry wines were set up as a function of their total phenolic content (for total phenol index, TPI<300 mg gallic acid per liter, dilution 2.5:10 to 5:10; for TPI>300 mg gallic acid per liter, dilution 1:10 to 3:10). Red wines absorb at the wavelength of measurement and dilutions between 0.35:10 and 0.1:10 are advisable. Reaction kinetics were also monitored and the antioxidant activity, expressed as Trolox Equivalent Antioxidant Capacity (TEAC), was determined at 2 and 15 min of reaction. The mean values for TEAC_2 min were 5.01±1.40 mM for red wines, 0.46±0.32 mM for white wines and 0.26±0.19 mM for Sherry wines. At 15 min, mean values were 6.93±2.41 mM for red wines, 0.67±0.47 mM for white wines and 0.26±0.19 mM for Sherry wines. The correlation coefficients were better at 2 min (r=0.9012) than at 15 min (r=0.8462) when compared with TPI. Hence, TEAC_2 min seems to be a more appropriate measure.     

Metal Chelates of Cerium (III), Thorium(IV) and Dioxouranium(VI) with Some Heterocyclic AZO Dyes; Potentiometric and Spectrophotometric Studies

ABSTRACT

The stepwise formation constants of Ce³⁺, Th⁴⁺ and UO₂ ²⁺ complexes with four azo compounds based on I-phenyl-2, 3-dimethylpyrazoline-5-one nucleus namely; 4-phenylazo- (2-hydroxy, 5-x) 1-pheny1-2, 3-dimethy1-pyrazoline-5-one, where x= H (1), OH (II), COOH (III) and NH₂ (IV) have been determined potentiometrically at different temperatures and ionic strengths in 30% (v/v) ethanol-water solutions, then the thermodynamic parameters are calculated.

Negatives values of both ∠H and ∠G are obtained indicating the exothermic and spontaneous nature of complexation reactions, whereas positive values of ∠S show that entropy consideration favour complex formation. The study at different ionic strengths shows that an increase in the latter causes a decrese in the pK values. The azo compounds are also tested as new reagents for the spectrophotometric determination of Ce³⁺, Th4⁺ and UO₂ ²⁺ ions in synthetic and natural solutions by extensive investigation of the optimum conditions favoring the formation of colored complexes.     

Metabolite Fingerprinting Using 1H-NMR Spectroscopy and Chemometrics for Classification of Three Curcuma Species from Different Origins

Curcuma longa, Curcuma xanthorrhiza, and Curcuma manga have been widely used for herbal or traditional medicine purposes. It was reported that turmeric plants provided several biological activities such as antioxidant, anti-inflammatory, hepatoprotector, cardioprotector, and anticancer activities. Authentication of the Curcuma species is important to ensure its authenticity and to avoid adulteration practices. Plants from different origins will have different metabolite compositions because metabolites are affected by soil nutrition, climate, temperature, and humidity. ¹H-NMR spectroscopy, principal component analysis (PCA), and orthogonal projections to latent structures-discriminant analysis (OPLS-DA) were used for authentication of C. longa, C. xanthorrhiza, and C. manga from seven different origins in Indonesia. From the ¹H-NMR analysis it was obtained that 14 metabolites were responsible for generating classification model such as curcumin, demethoxycurcumin, alanine, methionine, threonine, lysine, alpha-glucose, beta-glucose, sucrose, alpha-fructose, beta-fructose, fumaric acid, tyrosine, and formate. Both PCA and OPLS-DA model demonstrated goodness of fit (R² value more than 0.8) and good predictivity (Q² value more than 0.45). All OPLS-DA models were validated by assessing the permutation test results with high value of original R² and Q². It can be concluded that metabolite fingerprinting using ¹H-NMR spectroscopy and chemometrics provide a powerful tool for authentication of herbal and medicinal plants.     

新型吸附剂的合成、表征及其对Ni(II)的吸附研究

利用滴加法合成了球形含Ni^2＋交联壳聚糖, 并通过胺化引入大量活性氨基, 再经除镍制成对重金属镍离子具有较好吸附能力的新型吸附剂[P-C-CTS(Ni)]. 通过Ni^2＋吸附容量的测定, IR及XPS分析, 验证了合成技术路线的正确性. 通过研究pH值对吸附量的影响, 初步讨论了无柠檬酸根(Cit)配位体存在时, 吸附剂对Ni(II)的吸附为螯合作用. 通过Cit存在条件下(c_Ni＝c_Cit＝0.852 mmol•L^－1), 吸附剂对Ni(II)离子和Cit的吸附量随pH值的变化, 结合相应pH值下金属镍的形态分布, 探讨了其对Ni(II)的吸附机理, 研究认为不仅仅是简单的螯合作用, 其吸附机理和吸附量与溶液中金属离子的存在形式有关, 引入静电吸附原理解释了吸附剂对Ni(II)的吸附现象.     

S掺杂形式对TiO2基光催化剂结构和性能的影响

采用改进的Sol-gel法制备了S-TiO₂和TiO₂,用1 mol·L^-1的H₂SO₄对TiO₂进行表面修饰制成的SO₄^2-/TiO₂。采用XRD、IR、UV-Vis、SEM和EDS等技术对催化剂的结构进行了表征,以L酸(1-萘酚-5-磺酸)为目标物,考察了所制备的催化剂的性能．结果表明：S-TiO₂的禁带宽度明显降低,并且对400~650 nm区域的可见光都有一定的吸收,其可见光活性和紫外光活性均高于SO₄^2-/TiO₂和纯TiO₂。     

Comparison of LC-MS3 and LC-MRM Methods for Quantifying Amantadine and Its Application in Therapeutic Amantadine Monitoring in Human Plasma

A simple sample preprocessing method was developed for the quantitative determination of amantadine (AMT) in human plasma by liquid chromatography-tandem mass spectrometry cubed (LC-MS³). The LC-MS³ system comprised a Shimadzu Exion LC-20AD HPLC pump coupled with a QTRAP 5500 mass spectrometer. First, the plasma samples were pretreated using acetonitrile as the extracting solution to precipitate protein. Next, amantadine and amantadine-d₁₅ (AMT-d₁₅) were separated on an Agilent Poroshell 120 SB-C18 column (4.6 mm × 50 mm, 2.7 μm) using isocratic elution with solvent A (70% 0.1% formic acid) and solvent B (30% acetonitrile) at a flow rate of 0.8 mL/min. The total run time for each sample was 3 min. The system used triple-stage fragmentation transitions at m/z 152.2→135.3→107.4 for AMT quantification in the positive ion mode and m/z 167.0→150.3→118.1 for AMT-d₁₅ quantification. The LC-MS³ assay was linear (r > 0.995) with a concentration range of 50–1500 ng/mL. The lower limit of quantification (LLOQ) was 50 ng/mL, and the intra-day and inter-day accuracies and precisions were less than 8.0% at all concentrations. In addition, the recoveries and matrix effect for AMT in human plasma were within acceptable limits. In terms of stability, AMT had no significant degradation under all conditions. All the results met the requirements of the guidelines of the Food and Drug Administration (FDA) for biological method validation. The novelty of the MS³ assay was that it presented a methodology with higher selectivity and sensitivity. This method was successfully applied to 44 human plasma samples, and the obtained quantitative results were compared with another liquid chromatography-multiple reaction monitoring (LC-MRM) method. The Passing-Bablok regression coefficients and Bland-Altman plot revealed no difference between the LC-MS³ and LC-MRM methods, implying that the developed LC-MS³ method is a reliable and accurate assay for AMT determination in human plasma. These results are also a proof of concept for determining chemicals in biological samples by the LC-MS³ strategy.     

铽(Ⅲ)与PvdA作用的光谱研究

Pyoverdine A(PvdA)是荧光假单胞菌分泌的一种水溶性较高的黄绿色荧光铁载体。在50mmol·L^-1Tris-HCl,pH8.0条件下,使用紫外-可见吸收差光谱、荧光光谱研究了铽(Ⅲ)与荧光铁载体PvdA的结合。结果表明铽(Ⅲ)可与PvdA结合形成1：1的配合物,条件结合常数为(4.44±0.82)×10¹⁴mol^-1·L。在生理条件下,PvdA可竞争伴清蛋白N-,C-端结合的铽(Ⅲ)形成Tb-PvdA配合物;Tb-PvdA与荧光假单胞菌细胞表面受体FpvA结合形成Tb-PvdA-FpvA复合物。     

由六亚甲基四胺和柔性芳香羧酸构筑的两个一维配位聚合物的合成及晶体结构

利用六亚甲基四胺分别与苯氧乙酸、Cu(NO₃)₂·3H₂O及2,4-二氯苯氧乙酸、Zn(NO₃)₂·6H₂O反应,得到了2个新的一维配位聚合物,{[Cu₂(pa)₄](μ₂-hmt)}_n(1)和{{{[Zn₃(dcpa)₄(OH)]₂(μ₂-dcpa)₂}(μ₂-hmt)}·5H₂O}_n(2)(Hpa=苯氧乙酸,Hdcpa=2,4-二氯苯氧乙酸,hmt=六亚甲基四胺)。2个配合物均用元素分析、红外光谱、X射线单晶衍射及差热分析进行了表征。晶体结构分析表明,在配合物1中,4个苯氧乙酸根桥联2个Cu²⁺形成[Cu₂(COO)₄]双核结构,相邻的[Cu₂(COO)₄]双核单元由六亚甲基四胺桥联成一维的"zigzag"链;在配合物2中,6个2,4-二氯苯氧乙酸根和2个OH^-桥联6个Zn²⁺形成六核{[Zn₃(dcpa)₄(μ₃-OH)]₂(μ₂-dcpa)₂}结构单元,然后相邻的六核单元由2个六亚甲基四胺桥联成一维双链结构。     

不同直径改性PAN纳米纤维膜与Fe3+的配位反应及其配合物对有机染料降解的催化性能

使用静电纺丝技术和偕胺肟反应制备了三种不同直径的改性聚丙烯腈(PAN)纳米纤维膜,然后将它们作为配体分别与Fe3+进行配位反应制备改性PAN纳米纤维膜铁配合物,重点研究了三种改性PAN纳米纤维膜与Fe3+配位反应的动力学特性及其温度和Fe3+初始浓度的影响.最后将其作为非均相Fenton反应催化剂应用于染料降解反应中,考察了改性PAN纳米纤维膜直径对其催化活性的影响.结果表明,在所涉及的温度和浓度范围内,改性PAN纳米纤维膜与Fe3+之间配位反应不仅符合Langmuir和Freundlich吸附等温式,而且可理想地使用Lagergren准二级动力学方程进行描述,反应速率常数随着Fe3+初始浓度的增加而逐渐降低.在相同反应条件下,较小直径的纤维膜更容易与Fe3+发生配位反应,且反应速率常数和Fe3+配合量均随着纤维直径的降低而增大.不同直径改性PAN纳米纤维膜铁配合物在暗态条件下对染料的氧化降解反应表现出很好的催化活性,且在辐射光下其催化活性得到加强.改性PAN纳米纤维膜铁配合物的催化作用受到纤维直径的显著影响,由中等直径纳米纤维构成的配合物表现出最高的催化活性.     

基于硼二吡咯亚甲基类(BODIPY)衍生物的合成,光谱及汞离子识别(英文)

The synthesis and sensing properties of a new BODIPY derivative 1 are outlined. 1 shows fluorescence “turn-on” and colorimetric responses with high selectivity toward Hg²⁺ over the other metal cations. Coordination of Hg²⁺ influences the electronic properties of the receptor at meso-position and alter the efficiency of non-radiative decay, hence increase the fluorescence intensity and red shift the absorption spectrum.     

The spectral studies on the effect of Glu 101 to the metal binding characteristic of Euplotes octocarinatus centrin

Glu is highly conserved as the first amino acid of E-helix of the EF-hand protein. In this paper, Glu 101, the first amino acid of E-helix of the third EF-hand motif in Euplotes octocarinatus centrin (EoCen) was mutated to be Lys by the method of site direct mutation. Tb3+ and TNS were used as fluorescence probes in the study of the effect of this mutation to the metal binding characteristic of EoCen by fluorescence spectra. Results indicate that compared with EoCen, the mutation protein (E101K) displays a different Tb3+ binding characteristic and an increased hydrophobic exposure surface. Polyacrylamide gels electrophoresis indicated that the electrophoretic mobilities of EoCen and E101K are distinctly different. It can be deduced that the conformation of EoCen has been altered by this mutation. The general conditional binding constant of Tb3+ to the three loops of EF-hand sites I-III in E101K was calculated to be (5.64+/-0.57)x10(5)M(-1) according to the modified equation of the single binding process.     

The Impact of Grape Varieties to Wine Isotopic Characterization

This paper highlights the results of a study regarding the impact of geo-climatic conditions, the influence of grape varieties, and harvest year on the isotopic characterization of a wine from a specific vineyard area, using stable isotope ratio analysis by continuous flow mass spectrometry CF-IRMS. This analytical technique has made a significant contribution on wine characterization, by proving the botanical and geographical origin of the wine raw material.

A great variability was observed to sap ¹⁸O and ²H isotopic ratios for different types of vine (Vitis vinifera plant) from the studied area, Dealu Mare-Valea Calugareasca, reflecting the significant influence of variety on isotopic features. On the other hand, the comparison of stable isotopic fingerprints for rainfall water and sap revealed a close approximation value for ¹⁸O isotopic ratio, and an insignificant variation coefficient of ¹³C isotopic ratio in wine varieties (about 2.85%).

The results of isotopic characterization for grape vine sap and original wines for different varieties existing in Dealu Mare-Valea Calugareasca vineyard indicates the relevance of meteorological and viticulture parameters like precipitation, date of vintage, and grape cultivar for wine authentication process.