Hydroxyl radical

羟自由基
  • 文章类型: Journal Article
    双酚A(BPA)在水生环境中的广泛存在和使用已造成严重的生态破坏。煤矸石(CG),煤炭开采的副产品,由于其巨大的土地占用和潜在的污染,构成了主要的环境问题。成功合成了以煤矸石地质聚合物(CGP)为载体的磁性可回收地质聚合物(MnFe2O4-CGP),并对其类似Fenton降解BPA的能力进行了评估。表征技术揭示了球形MnFe2O4成功地掺入到CGP表面上,并且CGP是MnFe2O4固定和分散的极好平台。在pH=5、15mmol/LH2O2、0.6g/L催化剂下,60min内降解率达到100%,和50毫克/升的BPA,显著高于单独的MnFe2O4和CGP。结果表明,MnFe2O4-CGP复合材料中BPA的降解速率为0.1121min-1,符合一级动力学模型。MnFe2O4-CGP的饱和磁化强度为10.96emu/g,实现方便的恢复。MnFe2O4-CGP表现出优异的稳定性,因为BPA的降解率甚至在5个反应循环后仍保持在95%以上。这种效率可能是由于MnFe2O4-CGP诱导的反应性自由基的产生。淬灭和EPR自由基捕获实验明确证实了反应性自由基是羟基自由基(·OH)。这些结果表明,MnFe2O4-CGP作为磁性可循环地质聚合物复合材料在类Fenton催化中具有潜在的应用前景。
    The widespread presence and use of Bisphenol A (BPA) in aquatic environments has caused significant ecological damage. Coal gangue (CG), a byproduct of coal mining, poses a major environmental concern due to its vast land occupation and potential for pollution. A magnetic recyclable geopolymer (MnFe2O4-CGP) using coal gangue geopolymer (CGP) as the carrier was successfully synthesized and was evaluated for its ability to Fenton-like degrade BPA. The characterization techniques revealed the successful incorporation of spherical MnFe2O4 onto the CGP surface and that CGP serves as an excellent platform for the immobilization and dispersion of MnFe2O4. The degradation rate reached 100% within 60 min at pH = 5, 15 mmol/L H2O2, 0.6 g/L catalyst, and 50 mg/L BPA, significantly higher than MnFe2O4 and CGP alone. It was indicated that the degradation rate of BPA in MnFe2O4-CGP composites was 0.1121 min-1, which was consistent with the first-order kinetic model. The saturation magnetization of MnFe2O4-CGP was measured to be 10.96 emu/g, enabling convenient recovery. MnFe2O4-CGP exhibited excellent stability, as the degradation rate of BPA remained above 95% even after five reaction cycles. This efficiency may be due to the MnFe2O4-CGP induced generation of reactive radicals. Quenching and EPR radical trapping experiments unequivocally confirmed that the reactive radical was hydroxyl radical (•OH). These results indicate that MnFe2O4-CGP has potential application prospects as a magnetic recyclable geopolymer composite in Fenton-like catalysis.
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  • 文章类型: Journal Article
    设计并合成了连续双锁定发光铜纳米簇(CuNCs)探针,用于肿瘤细胞的特异性成像和选择性杀伤。该纳米探针是通过首先形成Fe3偶联的单宁酸(TA)稳定的CuNCs(CuNCs-FeIII)来制备的,由于CuNCs和Fe3+之间的电子转移而处于猝灭状态,然后在CuNCs-FeIII的表面上涂覆透明质酸(HA)的可保护层,以形成最终的双锁纳米探针(CuNCs-FeIII@HA)。当CuNCs-FeIII@HA靶的纳米探针通过CD44-HA受体进入肿瘤细胞时,HAase将首先消化纳米探针的HA层,然后,在肿瘤细胞中过表达的GSH会将Fe3+还原为Fe2+,从而恢复CuNCs的荧光发射,同时通过Fe2和H2O2之间的Fenton反应产生的羟基自由基(‧OH)杀死肿瘤细胞。这种CuNCs-FeIII@HA的连续双锁定发光纳米探针已成功用于肿瘤细胞的特异性成像和选择性杀伤。
    A sequential dual-locked luminescent copper nanoclusters (CuNCs) probe was designed and synthesized for the specific imaging and selective killing of tumor cells. This nanoprobe was prepared by first forming a Fe3+-coupled tannic acid (TA)-stabilized CuNCs (CuNCs-FeIII), which is in quenching state due to the electron transfer between CuNCs and Fe3+, and then coating a protectable layer of hyaluronic acid (HA) on the surface of CuNCs-FeIII to form the final dual-locked nanoprobe (CuNCs-FeIII@HA). When the nanoprobe of CuNCs-FeIII@HA target enter the tumor cells through CD44-HA receptor, HAase will first digest the HA layer of the nanoprobes, and then, GSH over-expressed in tumor cells will reduce Fe3+ to Fe2+, thus restoring the fluorescence emission of CuNCs and at the same time killing the tumor cells with the hydroxyl free radicals (∙OH) produced by the Fenton reaction between Fe2+ and H2O2. This sequential dual-locked luminescent nanoprobe of CuNCs-FeIII@HA has been successfully used for the specific imaging and selective killing of tumor cells.
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  • 文章类型: Journal Article
    柑橘素(CIT),一种由红曲霉产生的霉菌毒素,青霉,和其他真菌,会污染红曲米和其他食物,从而制约了它们的应用和发展。探索柑橘素的高效降解方法已成为研究热点之一。在这项研究中,citrinin的降解,受可见光(Vis)照射,紫外线(UV)光,模拟阳光,以及与过氧化氢(轻/H2O2)的组合,被调查。研究表明,紫外线,Vis,和模拟的阳光都对柑橘苷有一定程度的降解,降解效率与光源和光强度相关。有趣的是,当与100WVis和0.01MH2O2结合时,citrinin降解率增加到32%,与单独使用Vis和H2O2实现的1%和5%相比。羟基,由于在Vis下H2O2均匀开裂而产生,通过电子自旋共振测量进行了实验验证,可以通过亲核攻击加速citrinin的解离。采用密度泛函理论,通过比较citrinin的主要C原子的亲电子Parr函数(Pk)值,我们推断亲核·OH主要攻击C8和C5位点。本研究提出了一种通过结合可见光和H2O2快速高效地降解橘皮苷的方法。实际应用:这项研究提出了一种快速有效的方法,通过结合可见光和H2O2降解红曲米和其他含柑橘的产品中的柑橘素。
    Citrinin (CIT), a mycotoxin produced by Monascus, Penicillium, and other fungies, can contaminate red yeast rice and other foods, thus constraining their application and development. Exploring efficient degradation methods of citrinin is becoming as one of the hot research topics. In this study, the degradation of citrinin, irradiated by visible (Vis) light, ultraviolet (UV) light, and simulated sunlight alone, as well as in combination with hydrogen peroxide (light/H2O2), was investigated. The research demonstrates UV, Vis, and simulated sunlight all have a degree of degradation on citrinin, and the degradation efficiency correlates with light source and light intensity. Interestingly, when combined with 100 W Vis and 0.01 M H2O2, the citrinin degradation rate increases to 32%, compared to 1% and 5% achieved by Vis and H2O2 alone. Hydroxyl radicals, arising from the uniform cracking of H2O2 under Vis, were experimentally validated by electron spin resonance measurement and could accelerate the dissociation of citrinin by nucleophilic attacking. Employing the density functional theory, we deduced nucleophilic •OH mainly attack onto C8 and C5 site by comparing the electrophilic Parr functions (Pk+) value of main C atom of citrinin. This research presents a rapid and efficient degradation of citrinin by combining visible light with H2O2. PRACTICAL APPLICATION: This research presents a rapid and efficient method for the degradation of citrnin in red yeast rice and other citrnin containing products by combining visible light with H2O2.
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  • 文章类型: Journal Article
    气相氧化剂的非均相氧化是次级有机气溶胶(SOA)的重要化学转化途径,属性,以及气溶胶对气候和健康的影响。然而,我们对这种异质化学的了解仍然不足。在这项研究中,在低和高相对湿度(RH)条件下,研究了羟基(OH)自由基对α-pine烯臭氧分解SOA的非均相氧化,重点研究了SOA分子组成的演变及其对RH的依赖性。发现SOA在OH暴露水平下的非均相氧化相当于12小时的大气老化导致颗粒质量损失在25%RH下为60%,在90%RH下为95%。非均相氧化强烈改变SOA的分子组成。随着OH暴露的增加,二聚体与单体的信号比急剧增加,特别是在高RH条件下,这表明气溶胶水比二聚体更刺激单体与OH自由基的反应。此外,典型的SOA示踪化合物,如松酸,pinonic酸,羟基松糖酸和二聚体酯(例如,C17H26O8和C19H28O7)在典型大气条件下对非均相OH氧化的寿命为数小时,这突出了在使用基于示踪剂的方法估计单萜SOA浓度时需要考虑其异质损失。我们的研究揭示了单萜SOA的非均相氧化化学,并将有助于了解它们在大气中的演变和影响。
    Heterogeneous oxidation by gas-phase oxidants is an important chemical transformation pathway of secondary organic aerosol (SOA) and plays an important role in controlling the abundance, properties, as well as climate and health impacts of aerosols. However, our knowledge on this heterogeneous chemistry remains inadequate. In this study, the heterogeneous oxidation of α-pinene ozonolysis SOA by hydroxyl (OH) radicals was investigated under both low and high relative humidity (RH) conditions, with an emphasis on the evolution of molecular composition of SOA and its RH dependence. It is found that the heterogeneous oxidation of SOA at an OH exposure level equivalent to 12 hr of atmospheric aging leads to particle mass loss of 60% at 25% RH and 95% at 90% RH. The heterogeneous oxidation strongly changes the molecular composition of SOA. The dimer-to-monomer signal ratios increase dramatically with rising OH exposure, in particular under high RH conditions, suggesting that aerosol water stimulates the reaction of monomers with OH radicals more than that of dimers. In addition, the typical SOA tracer compounds such as pinic acid, pinonic acid, hydroxy pinonic acid and dimer esters (e.g., C17H26O8 and C19H28O7) have lifetimes of several hours against heterogeneous OH oxidation under typical atmospheric conditions, which highlights the need for the consideration of their heterogeneous loss in the estimation of monoterpene SOA concentrations using tracer-based methods. Our study sheds lights on the heterogeneous oxidation chemistry of monoterpene SOA and would help to understand their evolution and impacts in the atmosphere.
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  • 文章类型: Journal Article
    简介氧化应激,活性氧(ROS)产生和抗氧化防御之间的不平衡,在各种牙科疾病中起着重要作用。局部麻醉药经常用于牙科。牙科局部麻醉药的潜在抗氧化活性可有助于牙科实践。因此,本研究旨在探讨三种常用的牙科局部麻醉药的ROS清除活性,利多卡因,丙胺卡因,还有阿替卡因,重点研究它们对羟基自由基(HO•)和超氧阴离子(O2•-)的影响。材料和方法采用电子自旋共振(ESR)自旋捕获技术来专门测量不同浓度下这些局部麻醉剂的ROS清除活性。结果利多卡因,丙胺卡因,阿替卡因表现出浓度依赖性HO·-清除活性,IC50值为0.029%,0.019%,和0.014%,分别。利多卡因和丙胺卡因显示浓度依赖性O2•-清除活性,IC50值为0.033%和0.057%,分别。然而,阿替卡因未清除O2•-。结论积极使用局部麻醉药可通过直接清除ROS减轻氧化损伤和炎症损伤。然而,需要进一步的研究来阐明这些牙科局部麻醉药抗氧化作用的具体机制,以及它们对与氧化应激相关的牙科疾病的潜在影响.
    Introduction Oxidative stress, an imbalance between reactive oxygen species (ROS) production and antioxidant defenses, plays an important role in various dental diseases. Local anesthetics are frequently used in dentistry. The potential antioxidant activity of dental local anesthetics can contribute to dental practice. Therefore, this study aimed to investigate the ROS-scavenging activities of three commonly used dental local anesthetics, lidocaine, prilocaine, and articaine, focusing on their effects on hydroxyl radicals (HO•) and superoxide anions (O2 •-). Materials and methods The electron spin resonance (ESR) spin-trapping technique was employed to specifically measure the ROS-scavenging activities of these local anesthetics at varying concentrations. Results Lidocaine, prilocaine, and articaine exhibited concentration-dependent HO•-scavenging activities, with IC50 values of 0.029%, 0.019%, and 0.014%, respectively. Lidocaine and prilocaine showed concentration-dependent O2 •--scavenging activity, with IC50 values of 0.033% and 0.057%, respectively. However, articaine did not scavenge O2 •-. Conclusions The proactive use of dental local anesthetics may mitigate oxidative injury and inflammatory damage through direct ROS scavenging. However, further research is needed to elucidate the specific mechanisms underlying the antioxidant effects of these dental local anesthetics and their potential impact on the dental diseases associated with oxidative stress.
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  • 文章类型: Journal Article
    羟基自由基(OH)是高度反应性的,并且在生物系统内的许多生理和病理过程中起重要作用。羟自由基水平的异常变化与许多疾病相关,包括肿瘤,炎症和心血管疾病。因此,检测生物系统中的活性氧(ROS)并对其进行成像具有重要意义。在这项工作中,一种新型的荧光探针(HR-DL)已经被开发出来,同时瞄准两个细胞器。该探针基于香豆素-喹啉结构并表现出对羟基自由基(OH)的高选择性和灵敏度。当与OH反应时,氢提取过程释放了它的远程π共轭和ICT过程,导致波长大幅红移。这种探针具有良好的水溶性(在其氧化状态)的好处,响应时间短(10秒内),和独特的双重溶酶体/线粒体靶向能力。它已用于在生物系统和炎症小鼠模型中检测OH。
    The hydroxyl radical (OH) is highly reactive and plays a significant role in a number of physiological and pathological processes within biosystems. Aberrant changes in the level of hydroxyl radical are associated with many disorders including tumor, inflammatory and cardiovascular diseases. Thus, detecting reactive oxygen species (ROS) in biological systems and imaging them is highly significant. In this work, a novel fluorescent probe (HR-DL) has been developed, targeting two organelles simultaneously. The probe is based on a coumarin-quinoline structure and exhibits high selectivity and sensitivity towards hydroxyl radicals (OH). When reacting with OH, the hydrogen abstraction process released its long-range π-conjugation and ICT processes, leading to a substantial red-shift in wavelength. This probe has the benefits of good water solubility (in its oxidative state), short response time (within 10 s), and unique dual lysosome/mitochondria targeting capabilities. It has been applied for sensing OH in biosystem and inflammation mice models.
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  • 文章类型: Journal Article
    石墨烯量子点的合成富含特定的含氧基团(o-GQD)表现出良好的催化性能,为诊断和生物医学提供了一个有前途的工具,但是引入特定的氧基团仍然是一个挑战。这里,我们提出了一种温和的合成方案,用于通过Fe3O4催化的羟基自由基(·OH)氧化前体如氧化石墨烯,产生具有双催化功能的调节荧光发射(从蓝色到黄色)羰基官能化GQDs,聚苯胺(PANI)和聚多巴胺(PDA)。该方法可以在室温下进行比传统的高温氧化浓酸。有趣的是,o-GQD表现出优异的过氧化物酶(POD)-和抗坏血酸氧化酶样活性。XPS表征显示,与前体相比,o-GQDs中的羰基含量显着增加,甚至在发蓝光的铁掺杂GQDs(b-Fe-GQDs)中增加了14倍。在合成过程中引入Fe3O4会导致少量的Fe掺杂,通过与N配位提高B-Fe-GQDs的催化活性,开发了用于碱性磷酸酶检测的高灵敏度单信号和超选择性双信号方法。这种低成本和安全的合成策略为o-GQD的实际使用铺平了道路。
    The synthesis of graphene quantum dots-like enriched with specific oxygenated groups (o-GQDs) exhibiting great catalytic performance offers a promising tool for diagnosis and biomedicine, but introducing specific oxygen groups remains a challenge. Here, we propose a mild synthetic protocol for producing regulated fluorescence emission (from blue to yellow) carbonyl functionalized GQDs with double catalytic function through Fe3O4-catalyzed hydroxyl radical (·OH) oxidation the precursors like graphene oxide, polyaniline (PANI) and polydopamine (PDA). The method can be carried out at room temperature than the traditional high-temperature oxidation in concentrated acid. Interestingly, o-GQDs exhibit excellent peroxidase (POD)- and ascorbate oxidase-like activity. XPS characterization showed a significant increase in carbonyl content in o-GQDs compared to the precursor, even a 14-fold increase in blue-emitting iron-doped GQDs (b-Fe-GQDs). The introduction of Fe3O4 during the synthesis process results in a minor degree of Fe doping, which enhances the catalytic activity of b-Fe-GQDs through coordination with N. Based on this feature, highly sensitive single-signal and ultra-selective dual-signal methods for alkaline phosphatase detection were developed. This low cost and safe synthesis strategy paves the way for practical usage of o-GQDs.
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  • 文章类型: Journal Article
    羟自由基(·OH)清除能力(HOSC)的估算对于评估抗氧化剂至关重要,天然提取物,或针对临床疾病的药物。虽然纳米酶在相关应用中具有优势,它们仍然面临着活性和选择性的限制。作为回应,这项工作展示了制造的海带蛋白调制的锇(laminarin-Os)纳米簇(1.45±0.05nm),在为合理的HOSC估计量身定制的比色测定中充当过氧化物酶样纳米酶。这项研究验证了海带多糖的表征和显着的稳定性。通过利用海带蛋白Os丰富的表面负电荷和海带蛋白的表面羟基,促进氧化反应,增强laminarin-Os对3,3'的亲和力,5,5'-四甲基联苯胺(TMB)(KM=0.04mM)。这使得基于海带蛋白-Os的比色测定能够比柠檬酸盐更有效地响应·OH,白蛋白-,或其他基于多糖的Os。此外,实验结果还验证了在酸性条件下海带蛋白-Os的选择性过氧化物酶样行为。像抗坏血酸这样的抗氧化剂,谷胱甘肽,鞣酸,和半胱氨酸在比色平台中抑制652nm处的吸光度,使用海带蛋白-Os的过氧化物酶样活性。与商用套件相比,该测定显示出较高的灵敏度(例如,响应抗坏血酸0.01-0.075mM,谷胱甘肽1-15µg/mL,单宁酸0.5-5µM,和甘草酸单铵半胱氨酸1.06-10.63µM)和谷胱甘肽的HOSC测试,鞣酸,和甘草酸单铵半胱氨酸。总的来说,这项研究介绍了一种具有特殊的TMB亲和力和·OH选择性的新型Os纳米酶,为生物医学研究中的HOSC估计铺平了道路,药物分析,药品质量控制,和超越。
    Hydroxyl radical (·OH) scavenging capacity (HOSC) estimation is essential for evaluating antioxidants, natural extracts, or drugs against clinical diseases. While nanozymes offer advantages in related applications, they still face limitations in activity and selectivity. In response, this work showcases the fabrication of laminarin-modulated osmium (laminarin-Os) nanoclusters (1.45 ± 0.05 nm), functioning as peroxidase-like nanozymes within a colorimetric assay tailored for rational HOSC estimation. This study validates both the characterization and remarkable stability of laminarin-Os. By leveraging the abundant surface negative charges of laminarin-Os and the surface hydroxyls of laminarin, oxidation reactions are facilitated, augmenting laminarin-Os\'s affinity for 3,3\',5,5\'-tetramethylbenzidine (TMB) (KM = 0.04 mM). This enables the laminarin-Os-based colorimetric assay to respond to ·OH more effectively than citrate-, albumin-, or other polysaccharides-based Os. In addition, experimental results also validate the selective peroxidase-like behavior of laminarin-Os under acidic conditions. Antioxidants like ascorbic acid, glutathione, tannic acid, and cysteine inhibit absorbance at 652 nm in the colorimetric platform using laminarin-Os\'s peroxidase-like activity. Compared with commercial kits, this assay demonstrates superior sensitivity (e.g., responds to ascorbic acid 0.01-0.075 mM, glutathione 1-15 µg/mL, tannic acid 0.5-5 µM, and monoammonium glycyrrhizinate cysteine 1.06-10.63 µM) and HOSC testing for glutathione, tannic acid, and monoammonium glycyrrhizinate cysteine. Overall, this study introduces a novel Os nanozyme with exceptional TMB affinity and ·OH selectivity, paving the way for HOSC estimation in biomedical research, pharmaceutical analysis, drug quality control, and beyond.
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  • 文章类型: Journal Article
    我们研究了激光成丝诱导的脱氧核糖核酸(DNA)损伤,它是通过以1000Hz至10Hz的多个重复频率在水中聚焦飞秒近红外Ti:Sapphire激光而产生的。使用质粒DNA(pUC19),单链断裂,双股断裂,核碱基损伤,和片段化的DNA通过琼脂糖凝胶电泳进行分析和定量。此外,测定辐照后的H2O2浓度。我们观察到(1)每次激光发射的DNA损伤和(2)每次总DNA损伤的酶敏感碱基损伤随着激光重复率的增加而减少。此外,(3)很可能产生非常短的DNA片段,与使用X射线产生的相比,和(4)大多数OH自由基可以通过重组消除以产生H2O2,防止它们破坏DNA。链断裂形成的蒙特卡罗模拟表明,观察到的链断裂效率对激光重复率的依赖性主要是由于DNA分子的扩散。这些发现定量和定性地揭示了强激光脉冲诱导的特定DNA损伤谱不是由X射线诱导的,稀疏的电离辐射源。
    We investigated the deoxyribonucleic acid (DNA) damage induced by laser filamentation, which was generated by focusing femtosecond near-infrared Ti:Sapphire laser light in water at several repetition rates ranging from 1000 Hz to 10 Hz. Using plasmid DNA (pUC19), the single-strand break, double-strand break, nucleobase lesions, and the fragmented DNA were analyzed and quantified by agarose gel electrophoresis. Additionally, the H2O2 concentration after irradiation was determined. We observed that (1) the DNA damage per laser shot and (2) the enzyme-sensitive base lesions per total DNA damage decreased as the laser repetition rate increased. Furthermore, (3) extraordinarily short DNA fragments were likely to be produced, compared with those produced using X-rays, and (4) most OH radicals could be eliminated by recombination to generate H2O2, preventing them from damaging the DNA. The Monte-Carlo simulation of the strand break formation implies that the observed dependency of strand break efficiency on the laser repetition rate is mainly due to diffusion of DNA molecules. These findings quantitatively and qualitatively revealed that an intense laser pulse induces a specific DNA damage profile that is not induced by X-rays, a sparsely ionizing radiation source.
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  • 文章类型: Journal Article
    背景:山竹果皮多糖具有多种生物学活性,值得进一步研究。
    方法:UAEE-GMRP的抗氧化性能,UAEE-GMRP-1A,通过两种不同的抗氧化活性实验系统评估了CM-30和Ac-30。
    结果:四种多糖对羟自由基有较好的清除作用,而对脂质过氧化的抑制作用相对较弱。然而,总的来说,四种多糖在上述两个抗氧化实验中显示出一定程度的潜在应用,特别是来自藤黄果皮的化学改性多糖,从而有效地提高了它们的抗氧化活性。这也表明化学修饰是提高多糖活性的较好方法。此外,在这两个抗氧化剂探索实验中,与其他三种多糖相比,羧甲基化多糖显示出更强的活性。
    结论:羧甲基化修饰可能具有很大的应用潜力。
    BACKGROUND: Polysaccharide from Garcinia mangostana rind has many biological activities and deserves further research.
    METHODS: The antioxidant properties of UAEE-GMRP, UAEE-GMRP-1 A, CM-30, and Ac-30 were evaluated through two different antioxidant activity experimental systems.
    RESULTS: The four polysaccharides had a better scavenging effect on hydroxyl radicals, while their inhibitory effect on lipid peroxidation was relatively weak. However, overall, the four polysaccharides showed a certain degree of potential application in the two antioxidant experiments mentioned above, especially the chemically modified polysaccharides from Garcinia mangostana rind, which effectively improved their antioxidant activity. This also indicates that chemical modification is a better method to improve polysaccharide activity. In addition, in these two antioxidant exploration experiments, carboxymethylated polysaccharide showed stronger activity compared to the other three polysaccharides.
    CONCLUSIONS: The carboxymethylation modification may have great potential for application.
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