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.     

SDBS与HA缓蚀剂复配的实验与理论研究

通过静态失重法研究了十二烷基苯磺酸钠(SDBS)与六亚甲基四胺(HA)在盐酸溶液中对Q235钢的协同缓蚀效应, 并采用分子动力学模拟从缓蚀剂膜抑制腐蚀粒子扩散的角度对其缓蚀机理进行分析. 结果显示: SDBS和HA单独使用时, 最高缓蚀效率分别为82.82%和79.46%, 复配后最高缓蚀效率可达到92.78%; 与两种缓蚀剂单独使用时相比, SDBS与HA复配后缓蚀剂膜体系中的自由空间明显下降, 削弱了膜内缓蚀剂分子的自扩散能力, 腐蚀粒子在缓蚀剂膜携带下的被动迁移也随之减弱; SDBS与HA复配能更有效抑制腐蚀粒子在缓蚀剂膜中的扩散, 也就是说复配后的缓蚀剂具有更好的缓蚀性能.     

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.     

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.     

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.     

咪唑啉缓蚀剂在Fe(001)表面吸附行为的分子动力学模拟

采用分子动力学模拟方法研究了5种不同烷基链长的咪唑啉类缓蚀剂在Fe(001)表面的吸附行为和成膜机制,并对其缓蚀机理进行了深入分析.研究结果表明:咪唑啉分子的极性头基会吸附在金属表面上,而烷基碳链则背离金属表面,并通过自身的扭转形变实现稳定吸附;随着烷基链长的增加,缓蚀剂与金属基体的结合强度逐渐增加,所形成缓蚀剂膜的致密性也逐渐增大;致密的缓蚀剂膜能有效地阻碍腐蚀介质向金属表面扩散,从而达到延缓金属腐蚀的目的.5种缓蚀剂缓蚀性能的理论评价结果与实验结果吻合.     

新型不对称双季铵盐缓蚀剂在HCl中对Q235钢的缓蚀行为

采用静态失重法、极化曲线法和交流阻抗法研究了自制的含咪唑啉环不对称双季铵盐缓蚀剂(DBA)在1 mol•L^－1 HCl介质中对Q235钢的缓蚀性能, 并探讨了其在Q235钢表面的吸附行为. 结果表明, 缓蚀效率随DBA浓度增加而增大, 在25～55 ℃的实验温度范围内, 浓度为2.89×10^－4 mol•L^－1时, 缓蚀效率均在90%以上, 且缓蚀效率随温度升高而增大. 极化曲线测试显示DBA是一种阴极抑制为主的混合型缓蚀剂. 缓蚀剂在Q235钢表面的吸附过程为吸热过程, 其在Q235钢表面的吸附遵循Langmuir等温式, 属于化学吸附. 最后采用量子化学方法对DBA的缓蚀机理做了进一步分析.     

阳离子型可聚合咪唑类离子液体-丙烯酰胺共聚物的制备及其对盐酸腐蚀碳钢缓蚀行为

利用阳离子型可聚合离子液体1-丙烯酰氧乙基-3-甲基咪唑四氟硼酸盐与丙烯酰胺的反相微乳液共聚合,制备了阳离子型咪唑类离子液体-丙烯酰胺共聚物缓蚀剂,并探讨了其缓蚀性能。研究了不同阳离子度、不同浓度聚合物溶液的缓蚀性能以及吸附时间对盐酸腐蚀碳钢速率的影响,并初步讨论了缓蚀机理。研究表明,该种阳离子型缓蚀剂的缓蚀效率可达90%以上;缓蚀剂的缓蚀能力不仅取决于缓蚀剂的阳离子度,还取决于该种缓蚀剂的相对分子质量;缓蚀效率并非简单地随聚合物浓度的增加而提高,当聚合物溶液的浓度过高时,反而会使缓蚀效率下降;随吸附时间的延长,碳钢的腐蚀速率逐渐降低,约40 h后基本保持不变;加入缓蚀剂有效抑制了酸对铁的腐蚀,随缓蚀效率的提高,碳钢表面的粗糙程度明显降低,孔洞结构减少。     

硫酸溶液中聚天冬氨酸对碳钢的吸附缓蚀性能

应用电化学极化曲线和交流阻抗研究聚天冬氨酸(PASP)对碳钢的缓蚀性能,讨论了PASP浓度和温度对缓蚀效果的影响.结果表明:PASP是一种以抑制阳极为主的缓蚀剂.在实验温度范围内,PASP在0.5mol/L硫酸溶液中对碳钢的缓蚀效率随着温度升高而降低,并以10℃时的缓蚀效果最好.在给定温度下,缓蚀率均随PASP浓度的增加而迅速增加,但当PASP质量浓度达到2.5g/L时,缓蚀率的增加趋于平缓,10℃下,缓蚀率的最高值可达80.33%(PASP 6.0g/L),PASP在碳钢表面的吸附基本服从Freund lich吸附等温式,PASP的加入增大了碳钢的腐蚀反应表观活化能.     

1-(2-羟乙基)-2-烷基-咪唑啉缓蚀剂缓蚀机理的理论研究

采用量子化学计算、分子动力学模拟和分子力学相结合的方法, 对6种不同烷基链长的1-(2-羟乙基)-2-烷基-咪唑啉缓蚀剂抑制H2S腐蚀的缓蚀机理进行研究, 并对其缓蚀性能进行评价. 前线轨道分布和Fukui指数表明, 6种缓蚀剂分子的反应活性区域均集中在分子的咪唑环上, 3个反应活性中心分别位于咪唑环上的N(4), N(7)和C(8)原子, 可使咪唑环在金属表面形成多中心吸附. 分子的反应活性及活性区域分布对烷基链长并不敏感. 单分子吸附能、膜的内聚能、吸附角和链间距的计算数据显示, 缓蚀剂膜的稳定性以及膜与金属基体的结合强度随链长的增加而增大; 当正构烷基碳链长度大于13时, 缓蚀剂可在金属表面形成一层高覆盖度、致密的疏水膜, 能有效阻碍溶液中的腐蚀介质向金属表面扩散, 从而达到阻碍或延缓腐蚀的目的.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.