Deep eutectic solvent

低共熔溶剂
  • 文章类型: Journal Article
    制备了一种新型的磁性壳聚糖表面分子印迹聚合物(Fe3O4@CS@MIP),用于选择性识别和富集柚皮苷(NRG)。基于共价-非共价协同印迹策略制备了Fe3O4@CS@MIP,利用4-乙烯基苯基硼酸作为共价功能单体,低共熔溶剂(氯化胆碱/甲基丙烯酸[ChCl/MAA])为非共价功能单体,Fe3O4@CS纳米颗粒为磁性载体。所得Fe3O4@CS@MIP形貌均匀,优异的结晶度,优异的磁性能,和高表面积。由于双重识别能力,所得聚合物在磷酸盐缓冲液(pH7.0)中表现出优异的结合性能和快速的传质。发现Fe3O4@CS@MIP的最大结合量为15.08mgg-1,并且可以在180min内实现平衡吸附。此外,它们还表现出更强的NRG选择性和令人满意的可重用性,在5个吸附-解吸循环后只有11.0%的损失。此外,Fe3O4@CS@MIP,作为吸附剂,介绍了从柚皮中分离和富集NRG的实际应用潜力,提取效率在79.53%~84.63%之间。这项工作为改善MIP的性能提供了一种新策略,并为复杂样品中NRG的提取提供了有吸引力的选择。
    A novel and facile surface molecularly imprinted polymer coated on magnetic chitosan (Fe3O4@CS@MIP) was fabricated for the selective recognition and enrichment of naringin (NRG). The Fe3O4@CS@MIP was prepared based on covalent-noncovalent synergistic imprinting strategies, utilizing 4-vinyl phenyl boric acid as covalent functional monomer, deep eutectic solvent (choline chloride/methacrylic acid [ChCl/MAA]) as non-covalent functional monomer and Fe3O4@CS nanoparticles as the magnetic support. The obtained Fe3O4@CS@MIP exhibited a uniform morphology, excellent crystallinity, outstanding magnetic properties, and high surface area. Owing to the double recognition abilities, the resultant polymer showed exceptional binding performance and rapid mass transfer in phosphate buffer (pH 7.0). The maximum binding amount of Fe3O4@CS@MIP was found to be 15.08 mg g-1, and the equilibrium adsorption could be achieved within 180 min. Moreover, they also exhibited stronger selectivity for NRG and satisfactory reusability, with only 11.0% loss after five adsorption-desorption cycles. Additionally, the Fe3O4@CS@MIP, serving as an adsorbent, presented practical application potential in the separation and enrichment of NRG from pummelo peel, with extraction efficiency in the range of 79.53% to 84.63%. This work provided a new strategy for improving the performance of MIP and contributed an attractive option for the extraction of NRG in complex samples.
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  • 文章类型: Journal Article
    基于共晶点相图,通过混合一摩尔甲基三苯基溴化鳞(MTPPBr)和一摩尔龙胆酸(GA:2,5-二羟基-苯甲酸)来合成龙胆酸基深共晶溶剂(MTPPBr/GA-DES)。然后,用FT-IR表征,NMR,密度计,和TGA/DTA技术,并用作快速和绿色合成的有效和新型催化剂:(i)五种新的2(a-e)和五种已知的2(f-j)苯并[6,7]苯并[2,3-d]嘧啶和(ii)一种新的(3a)和11种已知的3(b-l)吡喃并[2,3-d]嘧啶,在无溶剂条件下,短反应时间,和高产量。值得一提的是,对于2(a-j)的合成,只有一个参考文献指出反应时间非常长(720-2400分钟),虽然在我们提出的策略中这些时间减少到大约35-50分钟,表明反应速率将快20-48倍,这是我们方法的明显和最明显的优势。
    A gentisic acid based-Deep Eutectic Solvent (MTPPBr/GA-DES) was synthesized by mixing one mole of methyl triphenylphosphonium bromide (MTPPBr) and one mole of gentisic acid (GA: 2,5-dihydroxy-benzoic acid) based on the eutectic point phase diagram. Then, it was characterized by FT-IR, NMR, densitometer, and TGA/DTA techniques and used as a potent and novel catalyst for the fast and green synthesis of: (i) Five new 2(a-e) and five known 2(f-j) benzo[6,7]chromeno[2,3-d]pyrimidines and (ii) One new (3a) and eleven known 3(b-l) pyrano[2,3-d]pyrimidines, in solvent-free conditions, short reaction times, and high yields. It is important to mention that for the synthesis of 2(a-j), there is only one reference which states that the reaction times are extremely long (720-2400 min), while these times are reduced to approximately 35-50 min in our proposed strategy, indicatinging that the rate of reactions will be 20-48 times faster, which is the clear and most obvious advantage of our approach.
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  • 文章类型: Journal Article
    背景:个性化医疗是一个快速发展的领域,为个体患者定制疾病治疗提供了新的机会。这种方法的主要思想是根据每个患者独特的药代动力学特征仔细选择安全有效的药物和治疗设备。异烟肼是一线抗结核药物,在其代谢过程中具有个体差异,导致接受等效剂量的患者之间血浆浓度存在显着差异。这种可变性需要创建个性化治疗方案作为个性化医学的一部分以实现更有效的治疗。
    结果:在这项工作中,首次建立了一种基于低共熔溶剂的液-液微萃取方法,通过高效液相色谱-紫外-可见检测法分离和测定人血浆中的异烟肼。提出了一种以百里酚为氢键供体,4-甲氧基苯甲醛为氢键受体的新型天然深共晶溶剂作为萃取溶剂。开发的微萃取程序在样品和萃取溶剂的混合过程中假定了两个同时过程:在4-甲氧基苯甲醛(天然深共晶溶剂的组分)存在下,极性分析物的衍生化形成疏水性席夫碱(1);席夫碱从样品相到萃取溶剂相的传质(2)。在最优条件下,检测限和定量限分别为20和60μgL-1。RSD值<10%,提取回收率为95%。
    结论:在这项工作中,首次提出了异烟肼在天然深共晶溶剂相中衍生化形成希夫碱的可能性。该方法提供了极性异烟肼的分离和预浓缩,而无需使用昂贵的衍生剂和固相萃取柱。希夫碱的形成通过质谱法确认。
    BACKGROUND: Personalized medicine is a rapidly revolving field that offers new opportunities for tailoring disease treatment to individual patients. The main idea behind this approach is to carefully select safe and effective medications and treatment plant based on each patient\'s unique pharmacokinetic profile. Isoniazid is a first-line anti-tuberculosis drug that has interindividual variability in its metabolic processing, leading to significant differences in plasma concentrations among patients receiving equivalent doses. This variability necessitates the creation of individualized treatment regimens as part of personalized medicine to achieve more effective therapy.
    RESULTS: In this work, a deep eutectic solvent-based liquid-liquid microextraction approach for the separation and determination of isoniazid in human plasma by high-performance liquid chromatography with UV-Vis detection was developed for the first time. A new natural deep eutectic solvent based on thymol as a hydrogen bond donor and 4-methoxybenzaldehyde as a hydrogen bond acceptor was proposed as the extraction solvent. The developed microextraction procedure assumed two simultaneous processes during the mixing of the sample and extraction solvent: the derivatization of the polar analyte in the presence of 4-methoxybenzaldehyde (component of the natural deep eutectic solvent) with the formation of a hydrophobic Schiff base (1); mass transfer of the Schiff base from the sample phase to the extraction solvent phase (2). Under optimal conditions, the limits of detection and quantification were 20 and 60 μg L-1, respectively. The RSD value was <10 %, the extraction recovery was 95 %.
    CONCLUSIONS: In this work, the possibility of isoniazid derivatization in the natural deep eutectic solvent phase with the formation of the Schiff base was presented for the first time. The approach provided the separation and preconcentration of polar isoniazid without the use of expensive derivatization agents and solid-phase extraction cartridges. The formation of the Schiff base was confirmed by mass spectrometry.
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  • 文章类型: Journal Article
    木质素,第二丰富的天然聚合物,是生物炼制和纸浆和造纸工业的副产品。进行这项研究是为了评估木质素的性质并评估使用木质素作为普通芦苇秸秆(芦苇)预处理的副产品的前景,其中使用各种成分的低共熔溶剂(DES):氯化胆碱/草酸(ChCl/OA),氯化胆碱/乳酸(ChCl/LA),和氯化胆碱/单乙醇胺(ChCl/EA)。木质素样品,以下简称Lig-OA,Lig-LA,和Lig-EA,在优化用DES预处理芦苇秸秆的条件后,获得了副产物,以提高随后的酶水解效率。使用凝胶渗透色谱法研究了木质素,UV-vis,ATR-FTIR,以及1H和13CNMR光谱;评估了其抗氧化活性,并对木质素/聚乙烯醇复合膜的紫外屏蔽性能进行了评价。DES组成对提取的木质素的结构和性质有显著影响。木质素清除ABTS+·和DPPH·自由基的能力,以及紫外线辐射屏蔽的效率,降低如下:Lig-OA>Lig-LA>Lig-EA。木质素含量为PVA重量的4%的PVA/Lig-OA和PVA/Lig-LA薄膜在UVA范围内阻挡了96%和87%的UV辐射,分别,并完全阻止UVB范围内的紫外线辐射。
    Lignin, the second most abundant natural polymer, is a by-product of the biorefinery and pulp and paper industries. This study was undertaken to evaluate the properties and estimate the prospects of using lignin as a by-product of the pretreatment of common reed straw (Phragmites australis) with deep eutectic solvents (DESs) of various compositions: choline chloride/oxalic acid (ChCl/OA), choline chloride/lactic acid (ChCl/LA), and choline chloride/monoethanol amine (ChCl/EA). The lignin samples, hereinafter referred to as Lig-OA, Lig-LA, and Lig-EA, were obtained as by-products after optimizing the conditions of reed straw pretreatment with DESs in order to improve the efficiency of subsequent enzymatic hydrolysis. The lignin was studied using gel penetration chromatography, UV-vis, ATR-FTIR, and 1H and 13C NMR spectroscopy; its antioxidant activity was assessed, and the UV-shielding properties of lignin/polyvinyl alcohol composite films were estimated. The DES composition had a significant impact on the structure and properties of the extracted lignin. The lignin\'s ability to scavenge ABTS+• and DPPH• radicals, as well as the efficiency of UV radiation shielding, decreased as follows: Lig-OA > Lig-LA > Lig-EA. The PVA/Lig-OA and PVA/Lig-LA films with a lignin content of 4% of the weight of PVA block UV radiation in the UVA range by 96% and 87%, respectively, and completely block UV radiation in the UVB range.
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  • 文章类型: Journal Article
    在目前的工作中,通过加热氢键受体(HBAs)四丁基溴化铵和四丁基溴化鳞,一步合成了低共熔溶剂(DESs),连同两个氢键供体(HBDs)乙醇胺和N-甲基二乙醇胺,以一定的摩尔比混合。然后将该混合物与水混合以形成DES+水系统。在大气压下,在293.15-363.15K的温度范围内,使用U管振荡方法成功测量了制备的DES水系统的密度。使用等容饱和技术研究了DES水系统的CO2捕集能力在压力范围为0.1MPa至1MPa,温度范围为303.15K至323.15KK,采用半经验模型拟合实验CO2溶解度数据,并计算了实验值与拟合值之间的偏差。在303.15K的温度和100kPa的压力下,TBAB和MEA的DES+水系统中的CO2溶解度,摩尔比为1:8、1:9和1:10时,测得为0.1430g/g,0.1479g/g,和0.1540g/g,分别。最后,结论是,与工业中常用的30%单乙醇胺水溶液相比,DES水系统具有更高的CO2捕集能力,表明DES+水系统用于CO2捕集的潜力。
    In the present work, deep eutectic solvents (DESs) were synthesized in a one-step process by heating the hydrogen bond acceptors (HBAs) tetrabutylammonium bromide and tetrabutylphosphonium bromide, along with two hydrogen bond donors (HBDs) ethanolamine and N-methyldiethanolamine, which were mixed in certain molar ratios. This mixture was then mixed with water to form a DES + water system. The densities of the prepared DES + water systems were successfully measured using the U-tube oscillation method under atmospheric pressure over a temperature range of 293.15-363.15 K. The CO2 trapping capacity of the DES + water systems was investigated using the isovolumetric saturation technique at pressures ranging from 0.1 MPa to 1 MPa and temperatures ranging from 303.15 K to 323.15 K. A semi-empirical model was employed to fit the experimental CO2 solubility data, and the deviations between the experimental and fitted values were calculated. At a temperature of 303.15 K and a pressure of 100 kPa, the CO2 solubilities in the DES + water systems of TBAB and MEA, with molar ratios of 1:8, 1:9, and 1:10, were measured to be 0.1430 g/g, 0.1479 g/g, and 0.1540 g/g, respectively. Finally, it was concluded that the DES + water systems had a superior CO2 capture capacity compared to the 30% aqueous monoethanolamine solution commonly used in industry, indicating the potential of DES + water systems for CO2 capture.
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  • 文章类型: Journal Article
    在慢性伤口治疗中,灭活组织的清创术和生物膜的根除必须在侵袭性与保护再生组织之间取得平衡。在这项研究中,尿素,一种有效的离液分子,通过与甜菜碱形成天然深共晶溶剂(NADES)来调节,以开发适用于受伤皮肤组织的新型清创材料(BU)。要评估BU的清创能力,连同其抗生物膜作用和生物相容性,采用临床前至临床方法。使用人工和临床淤泥样品进行的体外测定表明,BU具有很高的清创能力。此外,BU的去结构效应导致强大的抗生物膜能力,与防腐剂PHMB-甜菜碱或医用蜂蜜相比,细菌负荷减少,在人工腐皮和离体人皮肤中进行评估。此外,在糖尿病伤口的小鼠模型中评估BU的疗效,对清创和抗生物膜能力有显著影响,类似于在PHMB-甜菜碱和医疗蜂蜜处理的动物中观察到的那些。最后,BU在腿部溃疡中进行了临床评估,与蜂蜜相比,在减少细菌负荷和伤口面积方面表现出优势,没有不良影响。因此,BU代表可有助于慢性伤口护理的简单且非杀生物的选择。
    In chronic wound treatment, the debridement of devitalized tissue and the eradication of the biofilm must balance aggressiveness with care to protect regenerating tissues. In this study, urea, a potent chaotropic molecule, was modulated through the formation of a Natural Deep Eutectic Solvent (NADES) with betaine to develop a new debriding material (BU) suitable for application into injured dermal tissues. To evaluate BU\'s debriding capacity, along with its antibiofilm effect and biocompatibility, pre-clinical to clinical methods were employed. In vitro determinations using artificial and clinical slough samples indicate that BU has a high debriding capacity. Additionally, BU\'s de-structuring effects lead to a strong antibiofilm capability, demonstrated by a reduced bacterial load compared to the antiseptic PHMB-Betaine or medical honey, evaluated in artificial slough and ex vivo human skin. Furthermore, BU\'s efficacy was evaluated in a murine model of diabetic wound, demonstrating significant effects on debriding and antibiofilm capacity, similar to those observed in PHMB-Betaine and medical honey-treated animals. Finally, BU was clinically evaluated in leg ulcers, showing superiority in reduction of bacterial load and wound area compared to honey, with no adverse effects. Thus, BU represents a simple and non-biocidal option that could contributes to chronic wound care.
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  • 文章类型: Journal Article
    在这项研究中,由氯化胆碱制备的低共熔溶剂(DES),乳酸,和四种多元醇之一(乙二醇,甘油,木糖醇,和山梨糖醇)进行了比较,并评估了它们从龙虾壳中提取甲壳质的有效性。我们的结果表明,随着多元醇中羟基数量的增加,DES内的氢键网络变得更加密集。然而,这导致粘度相应增加,这影响了甲壳素的提取效率。在所有准备好的DES中,氯化胆碱-乳酸/甘油(CCLaGly)表现出优异的提取能力,从龙虾壳中提取纯甲壳素。纯度,结晶度使用CCLaGlyDES提取的几丁质的分子量与化学分离的几丁质的分子量相当,纯度达到94.76±0.33%,结晶度为78.78%,分子量为655kDa。此外,DES提取的几丁质的理化性质使用傅里叶变换红外光谱进行了表征,X射线衍射,热重分析,和扫描电子显微镜。本研究对多元醇对从龙虾壳中提取几丁质的影响进行了比较分析,从而为在可持续生物材料生产中利用各种甲壳类贝壳开辟了一条有希望的途径。
    In this study, deep eutectic solvent (DES) prepared from choline chloride, lactic acid, and one of the four polyols (ethylene glycol, glycerol, xylitol, and sorbitol) were compared and assessed for their effectiveness in extracting chitin from lobster shells. Our results revealed that as the number of hydroxyl groups in polyols increased, the hydrogen bond network within the DESs became denser. However, this led to a corresponding increase in viscosity, which impacted the efficiency of chitin extraction. Among all prepared DESs, choline chloride-lactic acid/glycerol (CCLaGly) exhibited superior extractive ability, resulting in the extraction of pure chitin from lobster shells. The purity, crystallinity, and molecular weight of the extracted chitin using CCLaGly DES were comparable to those of chemically-isolated chitin, with purity reaching 94.76 ± 0.33 %, crystallinity at 78.78 %, and a molecular weight of 655 kDa. Additionally, the physicochemical properties of the DES-extracted chitins were characterized using Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and scanning electron microscopy. This study conducted a comparative analysis of polyol effects on chitin extraction from lobster shells, thereby opening a promising avenue for the utilization of various crustacean shells in sustainable biomaterial production.
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  • 文章类型: Journal Article
    在这项研究中,我们提出了一种利用低共熔溶剂(DESs)作为萃取溶剂和分散液体的新策略,以纳米氧化锌(ZnO)为吸附剂。该方法结合了超声辅助基质固相分散体(UA-MSPD),用于提取六种活性成分(红景天苷,松果苷,acteoside,specnuezhenide,五味子中的五味子苷G13和齐墩果酸)。然后使用配备有二极管阵列检测器的高效液相色谱法分析提取物。各种参数的影响,如分散剂用量,DES卷,研磨时间,超声处理持续时间,和洗脱液体积对提取回收率的影响进行了研究,并在响应面法下使用中心复合设计进行了优化。优化条件的检出限为0.003至0.01mg/g,相对标准偏差为8.7%或更低。提取回收率在93%至98%之间变化。该方法对分析物表现出优异的线性(R2≥0.9997)。简单的,绿色,高效的DES/ZnO-UA-MSPD技术被证明是快速的,准确,对女贞子样品中6种活性成分的提取和分析是可靠的。
    In this study, we propose a novel strategy utilizing deep eutectic solvents (DESs) as both the extraction solvent and dispersing liquid, with nanometer zinc oxide (ZnO) serving as the adsorbent. This method incorporates ultrasound-assisted matrix solid phase dispersion (UA-MSPD) for the extraction of six active components (salidroside, echinacoside, acteoside, specnuezhenide, nuezhenoside G13, and oleanolic acid) from Ligustri Lucidi Fructus samples. The extracts were then analyzed using high-performance liquid chromatography equipped with a diode array detector. The effects of various parameters such as dispersant dosage, DESs volume, grinding time, ultrasonication duration, and eluent volume on extraction recovery were investigated and optimized using a central composite design under response surface methodology. The optimized conditions yielded detection limits ranging from 0.003 to 0.01 mg/g and relative standard deviations of 8.7% or lower. Extraction recoveries varied between 93% and 98%. The method demonstrated excellent linearity for the analytes (R2 ≥ 0.9997). The simple, green, and efficient DESs/ZnO-UA-MSPD technique proved to be rapid, accurate, and reliable for extracting and analyzing the six active ingredients in Ligustri Lucidi Fructus samples.
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  • 文章类型: Journal Article
    全氟烷基物质(PFAS)提取方法的现状提出了重大挑战,特别是对于具有不同碳链长度的多个PFAS。这项研究引入了一种能源驱动的战略方法,用于筛选深共晶溶剂(DES),以有效地去除各种PFAS,包括全氟烷基羧酸(PFCA),全氟链烷磺酸(PFSA),和全氟烷基酰胺(FAA),来自污染环境(共13种目标化合物)。利用基于能量的筛选,我们从共晶系统的1234种潜在起始材料中鉴定出对PFAS化合物光谱具有高亲和力的DES候选物。主要发现揭示了三丁基氧化膦/2-甲基哌嗪系统的优异去除效率,在实际环境水样中,具有不同碳链长度的各种PFAS超过99%。此外,我们通过从头算分子动力学(AIMD)模拟阐明了DES和PFAS之间的分子相互作用,为治理移除过程的机制提供有价值的见解。萃取机理涉及氢键网络拓扑和结构组织,DES能够提取PFAS,同时保持靶分子的弱聚集状态,并将对DES固有结构的影响降至最低。拟议的系统形成了一个动态的,互补,以及与PFAS的柔性非共价相互作用网络结构。这项研究推进了对DES作为可设计的理解,有效,以及用于PFAS修复的常规溶剂的可持续替代品,为环境化学和绿色技术做出重大贡献。
    The current landscape of perfluoroalkyl substances (PFAS) extraction methodologies presents significant challenges, particularly for multiple PFAS with different carbon chain lengths. This study introduced an energy-driven strategic approach for screening deep eutectic solvents (DESs) to effectively remove a diverse range of PFAS, including perfluoroalkylcarboxylic acids (PFCAs), perfluoroalkanesulfonic acids (PFSAs), and perfluoroalkyl amides (FAAs), from contaminated environments (total 13 target compounds). Utilizing energy-based screening, we identified DES candidates with high affinity for a spectrum of PFAS compounds from 1234 potential starting materials of eutectic systems. Key findings revealed the superior removal efficiency of tributylphosphineoxide/2-methylpiperazine system, exceeding 99 % for various PFAS with different carbon chain lengths in real environmental water samples. Additionally, we elucidated the molecular interactions between DESs and PFAS through ab initio molecular dynamics (AIMD) simulations, providing valuable insights into the mechanisms governing the removal process. The mechanism of extraction involves hydrogen bond network topology and structural organization, with DESs capable of extracting PFAS while maintaining a weakly aggregated state of target molecules and minimizing the impact on the intrinsic structures of DES. The proposed system forms a dynamic, complementary, and flexible non-covalent interaction network structure with PFAS. The study advances the understanding of DES as a designable, effective, and sustainable alternative to conventional solvents for PFAS remediation, offering a significant contribution to environmental chemistry and green technology.
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  • 文章类型: Journal Article
    微藻生物质在生产高价值副产物方面越来越受到重视。这项研究建议将小球藻微藻生物质整合到零废物生物精炼系统中,旨在生产生物柴油和生物肥料。它研究了超声辅助低共熔溶剂(DES)预处理和脂质回收以增强脂质提取的最佳条件。最佳DES预处理确定为1.6:1乙酸与氯化胆碱的摩尔比,0.36g生物质负荷,和2.50分钟的预处理。10分钟的提取时间和1:3的甲醇与丁醇体积比,脂质回收成功。这些条件产生的生物柴油质量脂质为139.52mg/g微藻生物质,具有出色的燃料特性。脱油的微藻生物质残留物显示出作为生菜生物肥料的希望,增强光合色素,但可能减少40%的产量。该研究还注意到根际微生物群落的变化,表明对有益微生物的刺激和抑制作用。这项研究有可能提高能源的可持续性,农业,和环境。
    Microalgal biomass is gaining increasing attention to produce high-value co-products. This study proposes integrating Chlorella microalgal biomass into a zero-waste biorefining system, aiming to produce biodiesel and biofertilizer. It investigates optimal conditions for ultrasound-assisted deep eutectic solvent (DES) pretreatment and lipid recovery to enhance the extraction of lipids. Optimal DES pretreatment was identified as a 1.6:1 acetic acid-to-choline chloride molar ratio, 0.36 g biomass loading, and 2.50 min of pretreatment. Lipid recovery succeeded with a 10-minute extraction time and a 1:3 methanol-to-butanol volume ratio. These conditions yielded biodiesel-quality lipids at 139.52 mg/g microalgal biomass with superior fuel characteristics. The de-oiled microalgal biomass residue exhibited promise as a lettuce biofertilizer, enhancing photosynthetic pigments but potentially reducing yields by 40 %. The study also notes changes in rhizosphere microbial communities, indicating both stimulatory and inhibitory effects on beneficial microbes. This study has the potential to enhance sustainability in energy, agriculture, and the environment.
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