complexation

络合
  • 文章类型: Journal Article
    具有高吸附容量和选择性的材料对于从富铵(NH4-N)废水中回收稀土元素(REES)至关重要。尽管新兴的金属有机框架(MOF)在REES回收中获得了广泛关注,在有限的吸附容量和选择性方面,存在尚未解决的科学困难,阻碍了其广泛的工程应用。在这项工作中,通过酰胺化反应制备二亚乙基三胺五乙酸(DTPA)改性的MOF材料(MIL-101(Cr)-NH-DTPA)。MIL-101(Cr)-NH-DTPA对La(III)(69.78mgg-1)的吸附能力增强,Eu(III)(103.01mgg-1)和Er(III)(83.41mgg-1)。材料的吸附等温线和物理化学表明,MIL-101(Cr)-NH-DTPA对REE的吸附是通过络合代替静电吸附实现的。这种络合反应主要由-COOH而不是-NH2或-NO2控制。同时,得到的材料即使在五个循环后仍保持其优异的活性。这种构造的吸附剂还对La(III)表现出优异的选择性吸附活性,Eu(III),和Er(III),在100至1500mg/L的NH4-N浓度下,去除效率达到70%。这项工作为从废水中回收稀土的吸附剂的开发提供了基本准则。
    The material with high adsorption capacity and selectivity is essential for recovering rare earth elements (REES) from ammonium (NH4+-N)-rich wastewater. Although the emerging metal-organic framework (MOF) has gained intensive attention in REES recovery, there are scientific difficulties unsolved regarding restricted adsorption capacity and selectivity, hindering its extensive engineering applications. In this work, a diethylenetriamine pentaacetic (DTPA)-modified MOF material (MIL-101(Cr)-NH-DTPA) was prepared through an amidation reaction. The MIL-101(Cr)-NH-DTPA showed enhanced adsorption capacity for La(III) (69.78 mg g-1), Eu(III) (103.01 mg g-1) and Er(III) (83.41 mg g-1). The adsorption isotherm and physical chemistry of materials indicated that the adsorption of REEs with MIL-101(Cr)-NH-DTPA was achieved via complexation instead of electrostatic adsorption. Such complexation reaction was principally governed by -COOH instead of -NH2 or -NO2. Meanwhile, the resulting material remained in its superior activity even after five cycles. Such a constructed adsorbent also exhibited excellent selective adsorption activity for La(III), Eu(III), and Er(III), with removal efficiency reaching 70% in NH4+-N concentrations ranging from 100 to 1500 mg L-1. This work offers underlying guidelines for exploitation an adsorbent for REEs recovery from wastewater.
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  • 文章类型: Journal Article
    为了获得废水中氨(NH4+)的高效消除,Cu(II),Ni(II),和Co(II))负载在Dowex-50WX8树脂(D-H)上,并研究了它们对水溶液中NH4的去除效率。与D-Ni2(qe=57.29mg/g)和D-Co2(qe=43.43mg/g)相比,D-H(D-Cu2)负载的Cu(II)对NH4(qe=95.58mg/g)的吸附容量最高。在各种实验条件下完成了针对利用D-Cu2去除NH4的详细研究。拟二级动力学模型较好地拟合了NH4+在D-Cu2+上的吸附数据。非线性Langmuir模型是吸附过程的最佳模型,在pH=8.4和303K时,在不到20分钟的时间内产生最大平衡吸附容量(qmax=280.9mg/g)。NH4+在D-Cu2+上的吸附是一个放热和自发的过程。在一个可持续的步骤中,从NH4吸附过程中得到的D-Cu(II)-ammine复合材料显示出优异的催化活性,可利用H2O2作为环保氧化剂降解苯胺蓝(AB)和甲基紫2B(MV2B)染料。
    To obtain high efficient elimination of ammonia (NH4+) from wastewater, Cu(II), Ni(II), and Co(II)) were loaded on Dowex-50WX8 resin (D-H) and studied their removal efficiency towards NH4+ from aqueous solutions. The adsorption capacity of Cu(II)-loaded on D-H (D-Cu2+) towards NH4+ (qe = 95.58 mg/g) was the highest one compared with that of D-Ni2+ (qe = 57.29 mg/g) and D-Co2+ (qe = 43.43 mg/g). Detailed studies focused on the removal of NH4+ utilizing D-Cu2+ were accomplished under various experimental conditions. The pseudo-second-order kinetic model fitted well the adsorption data of NH4+ on D-Cu2+. The non-linear Langmuir model was the best model for the adsorption process, producing a maximum equilibrium adsorption capacity (qmax = 280.9 mg/g) at pH = 8.4, and 303 K in less than 20 min. The adsorption of NH4+ onto D-Cu2+ was an exothermic and spontaneous process. In a sustainable step, the resulting D-Cu(II)-ammine composite from the NH4+ adsorption process displayed excellent catalytic activity for the degradation of aniline blue (AB) and methyl violet 2B (MV 2B) dyes utilizing H2O2 as an eco-friendly oxidant.
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  • 文章类型: Journal Article
    异糖精酸(HISA,或ISA的去质子化形式)是纤维素在碱性条件下的主要降解产物。它能与放射性核素和其他有毒金属离子形成强络合物,最终增强了它们在核废料处置库和其他环境系统中的流动性。99Tc是对氧化还原敏感的,在核反应堆中以高产率产生的长寿命裂变产物。在6≤pHm≤12.5和10-6M≤[ISA]≤0.2M的0.5MNaCl-NaISA-NaOH溶液中研究了99Tc(IV)的溶解度。根据溶解度数据得出了完整的化学和热力学模型,(pe+pHm)测量值,氧化还原形态,和固相表征。这些模型包括以前未报道的水性复合物TcO(OH)(ISA)2-和TcO(OH)2(ISA)22-。尽管Tc4+金属离子具有小尺寸和高极化率,在这项工作中描述的Tc(IV)-ISA配合物明显弱于其他与较大的M4+金属离子形成的ISA配合物,即,Zr,Pu和U。这种意外的行为可能可以通过Tc(IV)的强水解和TcO2部分的相应稳定来解释,其他M(IV)系统不会发生这种情况。这项工作中得出的热力学数据可以在核废料处理和其他环境应用的背景下在相关的地球化学计算中实施。
    Isosaccharinic acid (HISA, or ISA in its deprotonated form) is the main degradation product of cellulose under alkaline conditions. It can form strong complexes with radionuclides and other toxic metal ions, eventually enhancing their mobility in the context of nuclear waste repositories and other environmental systems. 99Tc is a redox-sensitive, long-lived fission product produced in high yield in nuclear reactors. The solubility of 99Tc(IV) was investigated in 0.5 M NaCl‒NaISA‒NaOH solutions with 6 ≤ pHm ≤ 12.5 and 10-6 M ≤ [ISA] ≤ 0.2 M. Complete chemical and thermodynamic models were derived on the basis of solubility data, (pe + pHm) measurements, redox speciation, and solid phase characterization. These models include the previously unreported aqueous complexes TcO(OH)(ISA)2‒ and TcO(OH)2(ISA)22-. In spite of the small size and high polarizability of the Tc4+ metal ion, the Tc(IV)-ISA complexes described in this work are significantly weaker than other ISA complexes formed with larger M4+ metal ions, i.e., Zr, Pu and U. This unexpected behavior can be possibly explained by the strong hydrolysis of Tc(IV) and corresponding stabilization of the TcO2+ moiety, which does not occur for other M(IV) systems. Thermodynamic data derived in this work can be implemented in geochemical calculations of relevance in the context of nuclear waste disposal and other environmental applications.
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  • 文章类型: Journal Article
    Co-无定形(CM)是提高不溶性药物水溶性的一种有前途的技术。但是在溶解过程中经常发生凝胶现象,严重威胁其溶解度/溶解性能。因此,设计良好的CM系统以减轻甚至避免凝胶现象的不利影响非常重要。在这项研究中,构建了紫杉素(TAX)和氧化苦参碱(OMT)的CM体系(TAX-OMTCMs),以提高TAX的溶解度和溶解性能。有趣的是,TAX-OMTCM在溶解过程中逐渐聚集并明显胶凝,但与结晶TAX相比,TAX-OMTCMs中TAX的溶解度和溶出度显著增强。因此,系统地探讨了TAX-OMTCMs凝胶化后的增溶机理。首先,通过相溶解度验证了TAX-OMTCM中两种组分之间的络合,荧光光谱法和等温滴定量热法。对于另一个,通过粉末X射线衍射彻底表征了溶解评估后TAX-OMTCM的残留固体,傅里叶变换红外光谱,扫描电子显微镜,这表明了TAX-OMTCMs的抗结晶性能。此外,分子模拟证明了TAX-OMTCMs单独和TAX-OMT复合物在水溶液中的分子间相互作用。最后,大鼠的药代动力学研究表明,口服后TAX-OMTCM(1:2)中TAX的生物利用度比结晶TAX高约5.5倍。总的来说,这项研究揭示了CM体系的络合和抗结晶作用对凝胶化后保持增溶行为的重要性,为提高药物CM系统的吸收性能提供了有效的策略。
    Co-amorphous (CM) is a promising technology for enhancing the aqueous solubility of insoluble drugs, but the gelation phenomenon has often occurred during the dissolution process and seriously threatened their solubility/dissolution performance. Therefore, it\'s quite important to design favorable CM systems to alleviate or even avoid the adverse effects of gelation phenomenon. In this study, CM systems of taxifolin (TAX) and oxymatrine (OMT) (TAX-OMT CMs) were constructed to improve the solubility and dissolution properties of TAX. Interestingly, TAX-OMT CMs gradually aggregated and obviously gelled during dissolution, but the solubility and dissolution of TAX in TAX-OMT CMs were significantly enhanced compared to crystalline TAX. Consequently, the underlying solubilization mechanisms of TAX-OMT CMs after gelation were systematically explored. For one thing, the complexation between the two components in TAX-OMT CMs was verified by phase solubility, fluorescence spectroscopy and isothermal titration calorimetry. For another, the residual solids of TAX-OMT CMs after dissolution evaluation were thoroughly characterized by means of powder X-ray diffraction, fourier transform infrared spectroscopy, scanning electron microscopy, which showed the anti-crystallization property of TAX-OMT CMs. Furthermore, molecular simulation demonstrated the intermolecular interactions of TAX-OMT CMs alone and TAX-OMT complexes in aqueous solution. Finally, pharmacokinetics study in rats suggested that the bioavailability of TAX in TAX-OMT CM (1:2) was approximately 5.5-fold higher than that of crystalline TAX after oral administration. Collectively, this study reveals the importance of complexation and anti-crystallization effects of CM systems on maintaining solubilization behavior after gelation, providing an effective strategy to improve the absorption performance of pharmaceutical CM systems.
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  • 文章类型: Journal Article
    从废水中回收稀土元素的研究日益受到重视。与其他方法相比,生物吸附是一个简单的,高效,和环保的稀土废水处理方法,具有更大的发展前景。本研究的目的是研究Yarrowialipolytica对五种稀土离子的生物吸附行为和机理(La3,Nd3,Er3,Y3,和Sm3by),特别关注生物吸附行为,生物吸附动力学,和生物吸附等温线。结果表明,在最佳条件下,Y的生物吸附能力为76.80mg/g。发现生物吸附过程符合伪二级动力学模型和Langmuir生物吸附等温线,表明Y.lipolytica采用单层化学生物吸附过程来生物吸附稀土离子。表征分析表明,参与稀土离子生物吸附的主要官能团为氨基,羧基,和羟基。通过表面络合促进了Y.Lipolytica对稀土离子的协同生物吸附,离子交换,和静电相互作用。这些发现表明,Y。lipolytica具有从废水中去除稀土元素的有效生物吸附剂的潜力。
    Research on the recovery of rare earth elements from wastewater has attracted increasing attention. Compared with other methods, biosorption is a simple, efficient, and environmentally friendly method for rare earth wastewater treatment, which has greater prospects for development. The objective of this study was to investigate the biosorption behavior and mechanism of Yarrowia lipolytica for five rare earth ions (La3⁺, Nd3⁺, Er3⁺, Y3⁺, and Sm3⁺) with a particular focus on biosorption behavior, biosorption kinetics, and biosorption isotherm. It was demonstrated that the biosorption capacity of Y. lipolytica at optimal conditions was 76.80 mg/g. It was discovered that the biosorption process complied with the pseudo-second-order kinetic model and the Langmuir biosorption isotherm, indicating that Y. lipolytica employed a monolayer chemical biosorption process to biosorb rare earth ions. Characterization analysis demonstrated that the primary functional groups involved in rare earth ion biosorption were amino, carboxyl, and hydroxyl groups. The cooperative biosorption of rare earth ions by Y. lipolytica was facilitated by means of surface complexation, ion exchange, and electrostatic interactions. These findings suggest that Y. lipolytica has the potential to be an effective biosorbent for the removal of rare earth elements from wastewater.
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  • 文章类型: Journal Article
    RO工艺通常用于处理和再利用含锰工业废水。然而,即使经过多阶段治疗,二级生化流出物仍然表现出高浓度的Mn2+,以及进入RO系统的有机物,导致膜污染。在这项工作中,系统分析了反渗透膜有机污染的过程和机理,考虑到Mn2+与腐殖酸(HA)共存,海藻酸钠(SA),牛血清白蛋白(BSA)及其混合物(HBS)。Mn2+对膜污染的影响为HBS>SA>HA>BSA,控制多糖污染物浓度应该是减轻膜污染的优先事项。在Mn2+与HA的存在下,SA,或HBS,膜污染主要归因于有机物和Mn2的络合以及界面相互作用能的促进。RO膜中BSA污染不受Mn2+的直接影响,Mn2+的加入引起了盐析效应,导致BSA在膜上的单个分子中沉积。同时,粘附能阻碍BSA在膜上的沉积,导致更温和的膜污染。本研究为Mn2+存在下RO膜有机污染的控制提供了理论依据和建议。
    RO process is commonly used to treat and reuse manganese-containing industrial wastewater. Nevertheless, even after undergoing multi-stage treatment, the secondary biochemical effluent still exhibits a high concentration of Mn2+ coupled with organics entering the RO system, leading to membrane fouling. In this work, we systematically analyze the RO membrane organic fouling processes and mechanisms, considering the coexistence of Mn2+ with humic acid (HA), sodium alginate (SA), bovine serum albumin (BSA) and their mixtures (HBS). The impact of Mn2+ on membrane fouling was HBS > SA > HA > BSA, controlling polysaccharide pollutant concentrations should be a priority for mitigating membrane fouling. In the presence of Mn2+ with HA, SA, or HBS, membrane fouling is primarily attributed to the complexation of organics and Mn2+ and the facilitation of interfacial interaction energy. RO membrane BSA fouling was not directly affected by Mn2+, the addition of Mn2+ induced a salting-out effect, leading to the deposition of BSA in a single molecular on the membrane. Simultaneously, adhesion energy hinders the deposition of BSA on the membrane, resulting in milder membrane fouling. This study provided the theoretical basis and suggestions for RO membrane organic fouling control in the presence of Mn2+.
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  • 文章类型: Journal Article
    目的:流体-流体界面表面活性剂分布的梯度可以诱导流体流动,称为Marangoni流。在生物和环境系统中发现的流体界面很少清洁,其中存在各种表面活性剂的混合物。多组分表面活性剂混合物的存在引入了成分之间相互作用的可能性,这可能会影响马兰戈尼的流动并改变流动动力学。
    方法:我们采用了流程可视化,表面张力和反应动力学测量,和数值模拟来定量研究反应表面活性剂混合物引起的Marangoni流动。不同的二元表面活性剂混合物用于比较分析。
    结果:表面活性剂相互作用对Marangoni流动的影响是通过观察不同的复杂流动模式来证实的,这些流动模式是由不同的组成比例和浓度的带相反电荷的表面活性剂的组合产生的。独特的流动模式源于混合表面活性剂时的成分依赖性界面现象。我们的发现提供了重要的见解,可用于指导有效的石油修复的发展或在受污染地区传播水性病原体。
    OBJECTIVE: The gradients in surfactant distribution at a fluid-fluid interface can induce fluid flow known as the Marangoni flow. Fluid interfaces found in biological and environmental systems are seldom clean, where mixtures of various surfactants are present. The presence of multi-component surfactant mixtures introduces the possibility of interactions among constituents, which may impact Marangoni flows and alter flow dynamics.
    METHODS: We employed flow visualization, surface tension and reaction kinetic measurements, and numerical simulations to quantitatively investigate the Marangoni flows induced by the reacting surfactant mixtures. Different binary surfactant mixtures were utilized for comparative analysis.
    RESULTS: The impact of surfactant interactions on Marangoni flows is confirmed through the observation of diverse complex flow patterns that result from the combination of oppositely charged surfactants in varying composition ratios and concentrations. Unique flow patterns originate from the composition-dependent interfacial phenomena upon mixing surfactants. Our findings provide vital insights that could be used to guide the development of effective oil remediation or the spreading of waterborne pathogens in contaminated regions.
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  • 文章类型: Journal Article
    溶解的铜和铁离子被认为是过氧单硫酸盐(PMS)活化的友好和经济的催化剂,然而,由于Cu(II)/Cu(I)和Fe(III)/Fe(II)循环的缓慢速率,Cu(II)和Fe(III)均不显示有效的催化性能。创新,当Cu(II)和Fe(III)偶联以激活硼酸盐(BA)缓冲液中的PMS时,我们观察到有机污染物的降解显着增强。罗丹明B(RhB,20µmol/L)在10分钟内达到96.3%,这高于单个Cu(II)-和Fe(III)-活化的PMS过程的总和。硫酸盐自由基,羟基自由基和高价金属离子(即,Cu(III)和Fe(IV))被确定为在Cu(II)/Fe(III)/PMS/BA系统中去除RhB的工作反应性物种,而最后一个扮演了主导角色。BA的存在极大地促进了Cu(II)通过与Cu(II)螯合而还原为Cu(I),然后通过Cu(I)还原Fe(III),导致Cu(I)和Fe(II)增强的PMS活化以及加速反应性物种的生成。此外,BA稳定溶液pH的强缓冲能力对于污染物的降解是令人满意的,因为微碱性环境有利于通过偶联Cu(II)和Fe(III)来活化PMS。一句话,这项工作提供了一个全新的见解,通过均匀的双金属和铁基高级氧化工艺在碱性条件下的扩展应用的杰出的PMS活化。
    Dissolved copper and iron ions are regarded as friendly and economic catalysts for peroxymonosulfate (PMS) activation, however, neither Cu(II) nor Fe(III) shows efficient catalytic performance because of the slow rates of Cu(II)/Cu(I) and Fe(III)/Fe(II) cycles. Innovatively, we observed a significant enhancement on the degradation of organic contaminants when Cu(II) and Fe(III) were coupled to activate PMS in borate (BA) buffer. The degradation efficiency of Rhodamine B (RhB, 20 µmol/L) reached up to 96.3% within 10 min, which was higher than the sum of individual Cu(II)- and Fe(III)- activated PMS process. Sulfate radical, hydroxyl radical and high-valent metal ions (i.e., Cu(III) and Fe(IV)) were identified as the working reactive species for RhB removal in Cu(II)/Fe(III)/PMS/BA system, while the last played a predominated role. The presence of BA dramatically facilitated the reduction of Cu(II) to Cu(I) via chelating with Cu(II) followed by Fe(III) reduction by Cu(I), resulting in enhanced PMS activation by Cu(I) and Fe(II) as well as accelerated generation of reactive species. Additionally, the strong buffering capacity of BA to stabilize the solution pH was satisfying for the pollutants degradation since a slightly alkaline environment favored the PMS activation by coupling Cu(II) and Fe(III). In a word, this work provides a brand-new insight into the outstanding PMS activation by homogeneous bimetals and an expanded application of iron-based advanced oxidation processes in alkaline conditions.
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  • 文章类型: Journal Article
    细菌对抗生素耐药性的持续发展是一个全球性挑战。因此,该领域的研究是必要的。为此目的需要分析技术。从这个角度来看,重点是原子吸收光谱法(AAS)。虽然它很旧,AAS通常提供意想不到的潜力。当然,这应该被利用。因此,目的是证明该技术在抗菌研究中的多功能性。这通过其实际应用的各种示例来说明。可以使用AAS,例如,为了确认抗菌化合物的身份,对于纯度控制,或量化药物制剂中的抗生素。后者允许分析而无需费力的样品制备并且不受其他赋形剂的干扰。此外,AAS可以帮助阐明作用模式或抵抗机制。在这种情况下,量化抗生素药物在(耐药)细菌细胞中的积累似乎起着重要作用。AAS的一般应用不仅限于含金属药物,还能测定一些有机化学抗生素。总之,这种观点提出了AAS在抗菌研究中的一系列应用,旨在提高对该方法的认识,从而可能有助于对抗抵抗。
    The ongoing development of bacterial resistance to antibiotics is a global challenge. Research in that field is thus necessary. Analytical techniques are required for such a purpose. From this perspective, the focus was on atomic absorption spectrometry (AAS). Although it is old, AAS often offers unexpected potential. Of course, this should be exploited. The aim was therefore to demonstrate the versatility of the technique in antibacterial research. This is illustrated by various examples of its practical application. AAS can be used, for example, to confirm the identity of antibacterial compounds, for purity controls, or to quantify the antibiotics in pharmaceutical preparations. The latter allowed analysis without laborious sample preparation and without interference from other excipients. In addition, AAS can help elucidate the mode of action or resistance mechanisms. In this context, quantifying the accumulation of the antibiotic drug in the cell of (resistant) bacteria appears to play an important role. The general application of AAS is not limited to metal-containing drugs, but also enables the determination of some organic chemical antibiotics. Altogether, this perspective presents a range of applications for AAS in antibacterial research, intending to raise awareness of the method and may thus contribute to the fight against resistance.
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  • 文章类型: Journal Article
    生物炭的功能性对同时存在的土壤和水系统中镉(Cd)和铅(Pb)共同污染的紧迫环境问题的影响尚未得到充分报道。本研究通过分批吸附和柱浸试验,研究了Fe和Mg功能化的小麦秸秆生物炭(Fe-WSBC和Mg-WSBC)对Cd和Pb吸附/固定的影响。重要的是,Fe-WSBC更有效地吸附Cd和Pb(82.84和111.24mgg-1),再生能力(去除效率94.32和92.365),与其他材料(WSBC和Mg-WSBC)相比,在竞争阳离子下的竞争能力(83.15%和84.36%)。Fe-WSBC对加标河水的实际可行性验证了在50mgL-1和100mgL-1污染中Cd的去除率为92.57%,Pb的去除率为85.73%,分别。此外,在流通条件下,Fe-WSBC对Cd和Pb的浸出降低到(0.326和17.62mgL-1),分别与对照(CK)(0.836和40.40mgL-1)相比。总之,这项研究提出了同时修复受污染的水和土壤基质的适用方法,提供对重金属共污染基质的环保绿色修复策略的见解。
    The impact of functionality of biochar on pressing environmental issue of cadmium (Cd) and lead (Pb) co-contamination in simultaneous soil and water systems has not sufficiently reported. This study investigated the impact of Fe- and Mg-functionalized wheat straw biochar (Fe-WSBC and Mg-WSBC) on Cd and Pb adsorption/immobilization through batch sorption and column leaching trials. Importantly, Fe-WSBC was more effective in adsorbing Cd and Pb (82.84 and 111.24 mg g-1), regeneration ability (removal efficiency 94.32 and 92.365), and competitive ability under competing cations (83.15 and 84.36%) compared to other materials (WSBC and Mg-WSBC). The practical feasibility of Fe-WSBC for spiked river water verified the 92.57% removal of Cd and 85.73% for Pb in 50 mg L-1 and 100 mg L-1 contamination, respectively. Besides, the leaching of Cd and Pb with Fe-WSBC under flow-through conditions was lowered to (0.326 and 17.62 mg L-1), respectively as compared to control (CK) (0.836 and 40.40 mg L-1). In short, this study presents the applicable approach for simultaneous remediation of contaminated water and soil matrices, offering insights into environmentally friendly green remediation strategies for heavy metals co-contaminated matrices.
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