温度对半胱氨酸缓蚀性能影响的实验评价与机理研究

通过实验对不同温度条件下半胱氨酸抑制盐酸对碳钢腐蚀的性能进行评价, 并采用分子动力学模拟(Molecular Dynamics Simulation, 简称MD)方法, 从缓蚀剂膜抑制腐蚀粒子扩散的角度对其缓蚀机理进行深入研究. 静态失重实验显示: 随温度的升高(25～65 ℃), 半胱氨酸缓蚀剂的缓蚀效率呈逐渐下降趋势, 其数值从88.36%降至61.64%. MD模拟发现: 随温度升高, 半胱氨酸缓蚀剂膜的自由体积逐渐增大, 且腐蚀粒子与缓蚀剂膜的相互作用也逐渐减弱, 更有利于腐蚀粒子在膜中的主动扩散; 同时膜内半胱氨酸分子的自扩散能力也随温度升高而增强, 腐蚀粒子在缓蚀剂膜携带下被动迁移的过程也随之加剧. 主动扩散和被动迁移两方面的变化表明, 腐蚀粒子在缓蚀剂膜中扩散能力随温度升高而增大; 也就是说, 随温度升高, 半胱氨酸缓蚀剂膜对腐蚀粒子的扩散抑制能力逐渐降低, 腐蚀粒子更易扩散运移至金属表面, 导致半胱氨酸缓蚀剂缓蚀效率的降低.     

温度对半胱氨酸缓蚀性能影晌的实验评价与机理研究

通过实验对不同温度条件下半胱氦酸抑制盐酸对碳钢腐蚀的性能进行评价,并采用分子动力学模拟(Molecular Dynamics Simulation,简称MD)方法,从缓蚀剂膜抑制腐蚀粒子扩散的角度对其缓蚀机理进行深入研究.静态失重实验显示:随温度的升高(25～65℃),半胱氨睃缓蚀剂的缓蚀效率呈逐渐下降趋势,其数值从88.36%降至61.64%.MD模拟发现:随温度升高,半胱氨酸缓蚀剂膜的自由体积逐渐增大,且腐蚀粒子与缓蚀剂膜的相互作用也逐渐减弱,更有利于腐蚀粒子在膜中的主动扩散;同时膜内半胱氨酸分子的自扩散能力也随温度升高而增强,腐蚀粒子在缓蚀剂膜携带下被动迁移的过程也随之加剧.主动扩散和被动迁移两方面的变化表明,腐蚀粒子在缓蚀剂膜中扩散能力随温度升高而增大;也就是说,随温度升高,半胱氨酸缓蚀剂膜对腐蚀粒子的扩散抑制能力逐渐降低,腐蚀粒子更易扩散运移至金属表面,导致半胱氨酸缓蚀剂缓蚀效率的降低.     

腐蚀介质在缓蚀剂膜中扩散行为的分子动力学模拟

采用分子动力学模拟方法,从缓蚀剂膜阻碍腐蚀介质粒子(H2O、H3O+和HCO3-)向金属表面扩散的角度,研究了4种1-R1-2-十一烷基-咪唑啉缓蚀剂(R1:羧甲基(A),羟乙基(B),氨乙基(C),氢(D))抑制碳钢CO2腐蚀的缓蚀机理,并对其缓蚀性能进行了理论评价.腐蚀介质粒子在不同缓蚀剂膜中的扩散系数、粒子与膜的相互作用能以及膜的自扩散性能的计算结果表明:4种缓蚀剂均可形成稳定的缓蚀剂膜,能有效阻碍腐蚀介质粒子向金属表面的扩散,达到抑制或延缓腐蚀的目的;随亲水支链(R1)极性的增加,缓蚀剂膜对腐蚀介质粒子扩散行为的抑制能力逐渐增强;同种缓蚀剂膜对正负离子H3O+和HCO3-比对中性的H2O分子具有更强的扩散抑制能力.综合计算及分析结果,4种缓蚀剂缓蚀性能的理论评价结果为ABCD,与文献实验结果吻合.     

咪唑啉缓蚀剂膜抑制腐蚀介质扩散行为的MD研究

采用分子动力学模拟的方法,对5种1-(2-氨乙基)-2-烷基-咪唑啉缓蚀剂[(NH2)C2H4-C3H4N2-CH2(CH2)nCH3,n=5,7,9,11,13]抑制CO2腐蚀的缓蚀机理进行了研究.计算了4种腐蚀介质粒子(H2O,H3O+,Cl-和HCO-3)在不同缓蚀剂膜中的扩散系数,并从自由体积分数、腐蚀介质粒子与缓蚀剂膜的相互作用、膜的自扩散性能等方面对缓蚀剂膜抑制腐蚀介质粒子扩散行为的微观机理进行了分析.扩散系数的计算结果表明:缓蚀剂膜能有效抑制腐蚀介质的迁移,削弱其腐蚀能力;与中性H2O分子对比,缓蚀剂膜对H3O+,Cl-和HCO-3带电离子的扩散具有更强的抑制效果;随烷基链长的增加,5种缓蚀剂膜对腐蚀粒子扩散的抑制能力呈增强趋势.综合分子动力学计算结果,5种缓蚀剂缓蚀性能随着烷基链长的增加逐渐增强,理论评价结论与实验结论相吻合.     

十二烷基苯磺酸钠在AZ31镁合金表面的吸附及其缓蚀作用

采用电化学阻抗谱(EIS)和极化曲线研究十二烷基苯磺酸钠(SDBS)对AZ31镁合金在3.5%(w, 质量分数)NaCl腐蚀介质中的吸附行为及缓蚀作用. 结果表明: SDBS可有效抑制AZ31镁合金在NaCl介质中的腐蚀, 其浓度为0.008 mol·L-1时缓蚀效率可达90%以上; 升高温度并不利于提高SDBS的缓蚀效率. SDBS在AZ31镁合金表面主要发生物理吸附, 吸附过程为放热、熵增的自发过程, 近似符合Langmuir单分子层吸附模型; SDBS为混合抑制型缓蚀剂, 但主要抑制阳极反应.     

缓蚀剂膜抑制腐蚀介质扩散行为的分子动力学模拟

采用分子动力学模拟方法研究了4种腐蚀介质粒子(H₂O, H₃O⁺, HS^-和Cl^-)在6种不同烷基链长的1-(2-羟乙基)-2-烷基-咪唑啉缓蚀剂膜中的扩散行为. 计算了腐蚀介质粒子在不同缓蚀剂膜中的扩散系数、膜的自由体积分数、粒子与膜的相互作用能等, 并对缓蚀剂膜抑制腐蚀介质粒子扩散行为的微观机理进行了分析. 计算结果表明, 6种缓蚀剂膜均可有效阻碍腐蚀介质粒子向金属表面的扩散, 从而达到抑制或延缓腐蚀的目的; 随烷基链长的增加, 缓蚀剂膜对腐蚀介质粒子扩散行为的抑制能力逐渐增强; 同种缓蚀剂膜对正负离子H₃O⁺, HS^-和Cl^-比对中性的H₂O分子具有更强的扩散抑制能力.     

绿色聚天冬氨酸复配缓蚀剂对A3碳钢的缓蚀抑雾作用

采用失重法和极化曲线法研究了聚天冬氨酸(PASP)和十二烷基酚聚氧乙烯醚(OP-10)复配对A3碳钢在6mol·L-1HCl腐蚀介质中的协同吸附行为及缓蚀抑雾作用.结果表明:复配缓蚀剂可有效抑制A3碳钢在HC1介质中的腐蚀,当PASP浓度为20g·L-1,缓蚀率可达94%,抑雾率83%;随着温度的升高,复配缓蚀剂的缓蚀性能下降.复合缓蚀剂在钢表面的吸附符合校正的Langmuir模型,吸附过程为放热、熵减的自发过程;复配体系属于阳极型缓蚀剂.     

氨基酸缓蚀剂在盐酸溶液中对钢的缓蚀作用

应用极化曲线、电化学阻抗谱等测试技术,研究了以谷氨酸作缓蚀剂在10%盐酸介质中对X65钢的缓蚀作用,测试腐蚀参数包括腐蚀电位(Ecorr)、极化电阻(Rp)、缓蚀效率(η)等.研究表明:该缓蚀剂是一种抑制阴极为主的混合型缓蚀剂,在较低的浓度具有良好缓蚀效果;缓蚀效率随着浓度的增加而提高,并在0.3g.L-1时达到最大值(90%以上).     

锌电极有机复配缓蚀剂的性能研究

应用极化曲线、表面张力、放电实验和SEM等测试方法,研究了阴离子表面活性剂十二烷基苯磺酸钠(简称SDBS)和非离子表面活性剂吐温-20(简称Tween)之复配体系(简称ST)在碱性介质中对锌电极电化学性能的影响及其作用机理.实验表明,复配缓蚀剂ST具有比单一添加SDBS或Tween更高的缓蚀效率,并且二者具有明显的协同作用,Tween在复配体系中的作用是使活性物质于锌电极表面的临界胶团浓度显著降低,吸附分布更加均匀.从而可更有效的抑制锌电极腐蚀,改善锌电极的表观形貌,达到延迟钝化的效果,使活性物质利用率得到显著提高.     

二乙基二硫代氨基甲酸钠在原油模拟液中对316L钢的缓蚀作用

配制原油模拟液,研究了二乙基二硫代氨基甲酸钠(SDDTC)于模拟液中单独使用以及分别与硫酸锌,铬酸钠的复配对316L钢的缓蚀效果.实验表明:在高酸高氯环境下,SDDTC能够很好地抑制316L钢的腐蚀;而且SDDTC与硫酸锌、铬酸钠之复配缓蚀剂具有很好的协同增效作用.这一相关研究具有重要的实际应用意义.     

Langmuir aggregation of Nile blue and safranine T on sodium dodecylbenzenesulfonate surface and its application to quantitative determination of anionic detergent.

We studied the interaction of sodium dodecylbenzenesulfonate (SDBS) with Nile Blue (NB) and Safranine T (ST) by a spectral correction technique. The aggregations of NB and ST on an SDBS surface obeyed Langmuir isothermal adsorption. The adsorption ratios of NB and ST to SDBS were both 0.5, and the adsorption constants of the aggregates were 1.80 x 10(5) and 9.49 x 10(4). The aggregations were applied to the quantitative determination of anion detergent in samples; the recovery of SDBS was between 90.3 and 106% together with an RSD of 3.78%.     

Influence of polymers on dust-related foam properties of sodium dodecyl benzene sulfonate with Foamscan

Foamability, liquid holdup, and foam appearance are key factors that determine dust control efficiencies. As the foam production method of the FoamScan instrument is similar to foaming device used for dust control, and its measurement means can satisfy the requirements of precise measuring, the FoamScan technology is adopted to explore the influence of xanthan gum (XG) and partial hydrolytic polyacrylamide (HPAM) on dust-related foam properties of sodium dodecyl benzene sulfonate (SDBS). It was found that with the increase of the polymer mass fraction, the liquid volume in the foam gradually increased. Additionally, the foaming time t₂₀₀ of the foaming agent decreased at first, then remained almost constant for both polymers, which indicated that the foamability and liquid holdup were enhanced by the addition of polymers into SDBS. In addition, the efficiencies of XG are higher than that of HPAM. The image analysis using the CSA software revealed that the mean radius formed by XG was smaller than that by HPAM and the number of bubbles was larger with XG than with HPAM. Thus, the XG foam has more area to contact with dust and could control dust better. The highly branched molecular structure and hydrogen bonds formed by XG played important roles in dust-related foam properties.     

Interaction of humic acids with human DNA: proposed mechanisms and kinetics

Human DNA quantification by quantitative real-time PCR (QRT-PCR) has gained great importance in forensic DNA and ancient DNA studies. However, in such samples, DNA quantification is impaired by the frequently present humic acid (HA). We have previously shown that the addition of synthetic HA inhibits QRT-PCR. In this study we investigated the possible mechanisms of HA interaction with human DNA, and kinetics of QRT-PCR inhibition. In QRT-PCR with pure human DNA and no HA added, VMAX was 40. With DNA sample containing 4 microg/mL of HA, VMAX was 30.30 while the addition of extra Taq polymerase to the same sample changed VMAX into 38.91, amplifying between 80 and 90% of input DNA. The KM/VMAX ratio in all the samples remained constant, indicating that the mechanism of HA inhibition of QRT-PCR is uncompetitive by nature. Moreover, HA shifts the human DNA melting temperature point (Tm) from 75 to 87 degrees C and inhibits DNase I-mediated DNA cleavage, most probably affecting the enzyme's activity.     

碱性溶液中锌电极缓蚀的研究

研究了硝酸铅（Pb(NO3)2）和十二烷基苯磺酸钠（SDBS）及二者组成的复合添加剂对在3mol•L-1 KOH溶液中锌电极电化学行为的影响, 结果表明:两种添加剂均具有一定的缓蚀作用,而其复合添加剂的协同效应、缓蚀效果最佳.     

不同聚合度聚乙二醇对A30碳钢的缓蚀性能

通过开路电位测量法、动电位极化曲线法和电化学阻抗谱法研究了表面活性剂聚乙二醇对A30碳钢的缓蚀作用,初步推测了其缓蚀机理．分别选取聚合度为600、2000、4000、6000的四种聚乙二醇进行实验,结果表明,聚乙二醇对碳钢的最高缓蚀率接近90％．聚乙二醇分子量对缓蚀作用有明显影响,相同浓度时聚合度越大,缓蚀性能越强．三种方法得到的结果具有同一性．     

一步法合成聚苯胺/十二烷基苯磺酸钠超疏水复合材料

在阴离子表面活性剂十二烷基苯磺酸钠(SDBS)体系中,采用一步法制得聚苯胺/SDBS超疏水复合材料.利用场发射扫描电子显微镜(FESEM)观察产物形貌并测定其元素组成.通过傅里叶变换红外光谱仪、紫外-可见光谱仪、X射线衍射等对其结构进行表征,用视频接触角测量仪测定材料的亲疏水性.考察SDBS浓度和溶液酸度对产物形貌及疏水性能的影响,探讨疏水机理.结果表明:在pH=1-9,SDBS浓度大于0.016 mol?L-1条件下,所制备复合材料的水接触角大于150°,SDBS掺杂使得苯胺单体的转化率高达98%.两亲分子SDBS亲水磺酸基与聚苯胺主链上的亚胺基不仅存在静电引力,而且能形成磺酰胺键,聚苯胺主链间又以氢键相互连接,SDBS分子的疏水烃基有序排列朝向聚苯胺主链外侧,从而组装形成具有微纳结构的聚苯胺/SDBS超疏水复合材料.本文结果有利于更好地理解聚苯胺/SDBS超疏水性复合材料的形成机理,对超疏水材料的设计提供新思路.     

十二烷基苯磺酸钠-硫酸耐而蓝体系的共振瑞利散射光谱及其分析应用

提出了共振瑞利散射法(RRS)测定十二烷基苯磺酸钠(SDBS)的新方法。在pH为1.98～3.29的B-R缓冲溶液中,硫酸耐而蓝与SDBS结合生成离子缔合物,使溶液共振瑞利散射(RRS)增强,其最大散射峰位于760 nm,另在533 nm、400 nm有两个较弱的散射峰。SDBS的浓度在0.04～1.6 mg/L范围内,与RRS强度有良好的线性关系,对SDBS的检出限(3σ)达0.018 mg/L。研究了适宜的反应条件和影响因素,表明该方法灵敏、稳定。用于环境水样中阴离子表面活性剂含量的测定,回收率为95.9%～106.7%。     

紫外分光光度计检测十二烷基苯磺酸钠鉴别潲水油的方法研究

建立了潲水油中十二烷基苯磺酸钠(SDBS)的检测方法,样品经高纯水提取、三氯甲烷萃取、亚甲蓝显色后,以紫外分光光度法进行测定。考察了提取温度、提取时间等因素的影响。实验结果表明,水对食用油中SDBS的最佳提取时间为2 h,温度为50℃,检测波长为645 nm。方法检出限(LOD)为0.1μg/kg。加标量分别为1.0、5.0、10.0、20.0μg/kg时的回收率为94%～96%,相对标准偏差(RSD)均小于5%。5组实际样品的检测结果显示,潲水油中SDBS的残留量平均值为19.19μg/kg,优质食用油中SDBS的平均含量为0.35μg/kg。潲水油中SDBS的含量有很大差别,但总体均高于优质食用油中的含量,方法可用于潲水油和食用植物油的鉴别。     

Hyaluronic‐Acid‐Presenting Self‐Assembled Nanoparticles Transform a Hyaluronidase HYAL1 Substrate into an Efficient and Selective Inhibitor

In this study, an original method of macromolecular design was used to develop a hyaluronidase‐1 (HYAL1) inhibitor from its principal substrate, hyaluronic acid (HA). HA‐based nanoparticles (HA‐NP) were obtained by copolymer self‐assembly and their effects on HYAL1 activity were investigated by combining different analytical tools. Compared to HA, HA‐NP exhibited an enhanced stability against HYAL1 degradation while maintaining its interaction with the HA receptors CD44 and aggrecan. HA‐NP displayed a strong and selective inhibition of HYAL1 activity and retarded the hydrolysis of higher‐molar‐mass HA in solution. A co‐nanoprecipitation process was used to formulate a range of hybrid nanoparticle samples, which demonstrated the specificity and efficiency of HA‐NP in HYAL1 inhibition.