聚（N，N＇-二乙基丙烯酰胺）水凝胶的制备及其溶胀动力学

以N,N’-二乙基丙烯酰胺（DEA）为单体,偶氮二异丁腈（AIBN）为引发剂,分别采用疏水性的1,2-二乙烯苯（DVB）和水溶性的N,N’-亚甲基双丙烯酰胺（BIS）为交联剂制备了温度敏感水凝胶聚（N,N’-二乙基丙烯酰胺）（PDEA）。制得的PDEA水凝胶的低临界溶解温度（LCST）在30℃附近,初步讨论了交联剂的用量和性质对水凝胶性能的影响。并对其在不同温度下达到溶胀平衡时的溶胀比,去溶胀动力学及干凝胶的再溶胀动力学过程进行了研究。     

聚(N,N′-二乙基丙烯酰胺)水凝胶的制备及其溶胀动力学

以N,N′-二乙基丙烯酰胺(DEA)为单体,偶氮二异丁腈(AIBN)为引发剂,分别采用疏水性的1,2-二乙烯苯(DVB)和水溶性的N,N′-亚甲基双丙烯酰胺(BIS)为交联剂制备了温度敏感水凝胶聚(N,N′-二乙基丙烯酰胺)(PDEA).制得的PDEA水凝胶的低临界溶解温度(LCST)在30 ℃附近,初步讨论了交联剂的用量和性质对水凝胶性能的影响.并对其在不同温度下达到溶胀平衡时的溶胀比,去溶胀动力学及干凝胶的再溶胀动力学过程进行了研究.     

前端聚合制备多孔聚丙烯酰胺水凝胶——溶剂和引发剂对反应和产物的影响

利用前端聚合结合发泡工艺制备了孔结构可调控的聚丙烯酰胺多孔水凝胶.研究发现溶剂和引发剂浓度变化对聚合前端的移动及形成的产物性能有重要影响.增加溶剂用量,聚合前端的移动速度和聚合前端最高温度下降,产物孔径增大,孔壁变厚,材料吸水溶胀性能降低;增加引发剂浓度,聚合前端移动速度显著加快,最高温度升高,产物的孔体积和溶胀率先增加后减小.     

P(NIPA-co-NVP)温敏性凝胶微粒的药物释放与降解

本文采用N-异丙基丙烯酰胺(NIPA)与N-乙烯基吡咯烷酮(NVP),以N,N-亚甲基双丙烯酰胺(MBA)为交联剂,氧化-还原试剂引发,通过反相悬浮共聚制备了微粒状热缩温敏水凝胶;研究了共聚单体配比及交联剂用量对凝胶温敏性能和溶胀性能的影响,并利用其温敏性以水杨酸为模型药物进行了药物吸附-释放实验;利用红外光谱和显微技术对微凝胶的结构和形态进行了表征,并初步探讨了该凝胶降解的可能性。实验发现:NVP单体的加入使共聚凝胶的体积相变温度和平衡溶胀率都明显升高,药物吸附率增加,而溶胀-退溶胀的响应速度及水保留率降低,释药率降低;该凝胶在pH1,37℃条件下能够降解,降解率随单体中NVP含量的增加而增加,随交联剂用量的增加而降低。     

双重交联VSNPs-PAA纳米复合水凝胶的制备及其溶胀性能的研究

采用自由基聚合法合成了乙烯基硅纳米粒子-聚丙烯酸(VSNPs-PAA)双重交联复合水凝胶,考察了交联剂、引发剂、单体以及p H值、温度、盐溶液等对水凝胶溶胀行为的影响。结果表明,引发剂浓度为0.08%,交联剂浓度为0.1%,单体浓度为80%时,合成的水凝胶溶胀性能最大,吸水率达到5000%以上;该水凝胶不仅具有p H值敏感性和p H值变化下良好的反复性,而且在p H4的酸性溶液中表现出温度敏感性,其溶胀率随温度的升高而增大;水凝胶的溶胀率随着盐溶液浓度的增大而减小。     

丙烯酸盐与丙烯酰胺共聚制备耐盐性高吸水树脂

以N,N-亚甲基双丙烯酰胺为交联剂,过硫酸铵-亚硫酸钠为引发剂,采用水溶液聚合法合成了耐盐性高吸水树脂-聚(丙烯酸钠-co-丙烯酰胺).研究了单体配比、丙烯酸中和度、引发剂及交联剂用量以及反应温度对常压及加压(1.96×103Pa)下吸盐水(wNaCl=0.009)率的影响.并对其结构进行了表征.该耐盐性高吸水树脂常压和加压下吸盐水率分别为50g·g-1和18 g·g-1,且凝胶强度好.     

粉煤灰复合聚丙烯酸钠凝胶的制备及其溶胀性能

粉煤灰(CFA)存在的情况下,采用自由基溶液聚合法,以过硫酸钾(KPS)为引发剂,N,N'-亚甲基双丙烯酰胺(NNMBA)为交联剂,制备了粉煤灰复合聚丙烯酸钠凝胶(CFAPAANa)。 以丙烯酸单体质量为基准,当交联剂用量为0.08%,引发剂用量为0.4%,粉煤灰用量为3%,丙烯酸中和度为70%,聚合温度为70 ℃时,所合成的粉煤灰复合聚丙烯酸钠凝胶在蒸馏水和生理盐水中平衡溶胀比最高,分别为1556(g/g)和168(g/g)。 考察了复合凝胶在不同介质溶液中的溶胀动力学,保水性能以及在土壤中的降解行为。 溶胀动力学研究表明,蒸馏水中溶胀初期复合凝胶聚合物链段的扩散运动能够调控凝胶溶胀的快慢及程度,而生理盐水中水分子的平移和对流运动在凝胶的溶胀过程中起着关键性作用。 保水和降解实验结果表明,25 ℃时,50 h凝胶保水率为64%,土壤中50 d时降解率达60%。 相比于聚丙烯酸钠凝胶,粉煤灰复合凝胶保水率提高了8%。     

聚(2-丙烯酰胺基-2-甲基丙磺酸/丙烯酰胺)水凝胶合成与性能研究

以2-丙烯酰胺基-2-甲基丙磺酸和丙烯酰胺为原料,以PEG6000为成孔剂,采用水溶液法合成多孔性聚(2-丙烯酰胺基-2-甲基丙磺酸/丙烯酰胺)水凝胶,研究了凝胶的溶胀性和电场作用下的退溶胀性能.在凝胶制备过程中,PEG6000分子充当成孔剂,通过综合性能比较和红外光谱测试可知,所得凝胶具有多孔结构,这种孔洞结构有利于水分子的进出.结果显示,当引发剂为0.005 mol/L,交联剂为0.008 mol/L,摩尔比AMPS:PEG6000=100∶1,AMPS:AAm=2∶1时,可得综合性能较好的PAMA凝胶.     

P(AMPS-co-HEMA)凝胶的合成与吸银性能研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和甲基丙烯酸羟乙酯(HEMA)为单体,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,过硫酸钾(KPS)为引发剂,采用自由基水溶液聚合法制备P(AMPS-co-HEMA)共聚凝胶,通过傅里叶红外光谱(FT-IR)对材料结构进行了表征.研究单体配比、交联剂的用量、引发剂的用量对共聚凝胶吸水性能的影响,并在此基础上对凝胶的溶胀、吸银及消溶胀性能进行研究.结果表明,当单体摩尔比n(AMPS)∶n(HEMA)=2∶1,交联剂用量ω(MBA)=0.6％,引发剂用量ω(KPS)=0.8％,所制得的凝胶吸水性能最好;凝胶在蒸馏水中的溶胀过程属于松弛平衡扩散;凝胶在AgNO3溶液中60min左右达到消溶胀平衡,且当AgNO3溶液的浓度为0.05mol/L时,银离子吸附量最大,为0.04g/g,消溶胀速率最快.     

聚乙烯醇/丙烯酸共聚物水凝胶的制备及溶胀性

制备了具有pH敏感性的聚乙烯醇(PVA)/丙烯酸(AA)共聚物水凝胶,研究了PVA与AA之间配比、交联剂、引发剂用量对凝胶转化率的影响,对水凝胶的溶胀行为和pH敏感性也进行了详细研究.实验表明PVA与AA的质量比为(1∶9)~(3∶7)之间时,引发剂和交联剂分别为PVA和AA总量的0.2%和0.3%时,凝胶转化率高.随着水溶液pH值从3增加到9,凝胶的溶胀比也相应的增加,表现出明显的pH敏感性.     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.