亲水性p-乙酰氨基酚树脂对茶碱的吸附性能

用氯球和p-乙酰氨基酚合成了亲水性p-乙酰氨基酚树脂(简记为GQ-01),研究乙酰氨基和酚羟基两类氢键作用位点修饰的GQ-01树脂对茶碱的吸附性能。实验表明:在相同茶碱起始浓度下,GQ-01树脂对茶碱的吸附量是XAD-4商业树脂对茶碱吸附量的1.9倍;GQ-01树脂对茶碱的吸附为放热、自发的过程;GQ-01树脂对茶碱的吸附动力学数据符合Lagergren一级速率方程,颗粒内扩散是吸附速率的主要控制步骤,GQ-01树脂对茶碱的吸附动力学可采用HSDM模型加以描述;GQ-01树脂对茶碱的动态吸附及脱附实验表明GQ-01树脂对水溶液中茶碱的饱和吸附量达到102.13mg/mL,树脂可以通过80%C2H5OH和1mol/L HCl的混合溶液再生。     

大孔树脂对对硝基苯胺的吸附行为及其应用研究

研究了溶液中无机盐、pH值对氨基修饰超高交联大孔树脂NDA-99、氧修饰超高交联大孔树脂NDA-150和大孔树脂XAD-4吸附对硝基苯胺的影响。结果表明,无机盐对吸附影响不大;NDA-99、NDA-150在中性范围吸附量最大,XAD-4的吸附量随pH增大而增大;3种树脂的吸附等温线都能很好的利用Freundlich方程进行拟合,吸附皆为放热反应且为优惠吸附;3种树脂的饱和吸附量大小依次为NDA-150>NDA-99>XAD-4。依据上述结论,采用NDA-150处理对硝基苯胺生产母液废水,每批次处理量为40BV,废水中对硝基苯胺浓度由2130mg/L降至9.6mg/L,去除率达99.5%,吸附后的树脂采用95%的乙醇可完全再生,高浓度对硝基苯胺乙醇再生溶液经蒸馏可回收对硝基苯胺和脱附剂,实现了废水治理与资源化的统一。     

邻硝基苯甲醚生产废水预处理工艺的研究

采用"酸化-树脂吸附"法对邻硝基苯甲醚生产废水进行预处理研究。比较了XAD-4、NDA-88、NDA-99、NDA-150几种树脂对酸化后废水中邻硝基苯酚的静态吸附行为,并选用吸附量较大的NDA-150树脂对该废水进行了吸附及脱附研究。结果表明,pH为4时,NDA-150树脂的平衡吸附量4.38mmol/g。动态吸附处理量为40BV(树脂体积)时,酚去除率95%,以8%NaOH为脱附剂,温度333K,脱附率98%。该工艺CODCr总去除率92%,邻硝基苯酚总去除率99%,每升废水可回收邻硝基苯酚10.8g,纯度大于97%。     

复合功能吸附树脂对2,4-二硝基苯酚的吸附特性

研究了NDA-99复合功能吸附树脂对2,4-二硝基苯酚的吸附及脱附行为.结果表明,该树脂对2,4-二硝基苯酚的吸附与脱附效果较好.在283-313K和研究的浓度范围内,吸附行为符合Freundlich和Langmuir等温式,该树脂对2,4-二硝基苯酚的动态吸附量为161.8mg/g.用质量分数为10%NaOH溶液作脱附剂,温度333K,体积为5BV(床体积)时,脱附率为96.7%,树脂可反复使用,并回收2,4-二硝基苯酚.     

酚羟基修饰的超高交联聚苯乙烯树脂对苯酚吸附及脱附性能的研究

对超高交联聚苯乙烯树脂进行酚羟基修饰得到修饰后的超高交联聚苯乙烯树脂(JN-2),将该树脂与大孔吸附树脂(Amberlite XAD-4)和超高交联树脂(NDA-150)在水溶液中对苯酚进行吸附-脱附性能比较,经过酚羟基修饰的超高交联聚苯乙烯树脂(JN-2)对苯酚的吸附性能有所提高,同时脱附性能明显改善,该树脂可望在含酚废水治理中得到广泛应用.     

大孔树脂对磺酸类化合物吸附行为的研究

用4种大孔树脂ND-022，ND-900，NDA-99和NDA-100作为吸附剂，分别对水溶液中甲基磺酸钠、苯磺酸钠、对甲基苯磺酸钠和2-萘磺酸钠等磺酸盐进行吸附．探讨了溶液的初始pH值对不同类型树脂吸附磺酸类物质的影响，并通过动态吸附实验研究了SO4^2-对树脂吸附磺酸盐的影响．实验结果表明，复合功能树脂NDA-99对磺酸类化合物具有良好的吸附性能，且其选择性优于弱碱树脂ND-900，这为进一步研究大孔树脂对磺酸类物质的吸附机理和实际工业应用提供了一定的理论依据。     

氨基吡啶修饰的高交联树脂合成与吸附性能

以氯球为原料,二氯乙烷为溶剂,FeCl_3为催化剂,利用Friedel-Crafts反应制备甲苯超高交联树脂,测其氯含量为6.38%。为降低氯含量和提高吸附性能,采用2-氨基吡啶对该高交联树脂进行化学修饰,获得的高交联树脂(记为GQ-08)氯含量下降为1.36%,然后详细研究了GQ-08对水杨酸的吸附性能。实验结果表明,GQ-08在p H 2.75时对水杨酸的吸附容量最大,达到310.7 mg·g~(-1);GQ-08对水杨酸的吸附是放热过程,吸附等温线服从Freundlich方程;当溶液中NaCl含量由0%到2%变化时,GQ-08对水杨酸的吸附量明显减少,说明氯离子与水杨酸存在竞争吸附作用,增加盐度不利于水杨酸吸附。因此,在利用GQ-08树脂进行水杨酸富集分离或处理生产废水回收水杨酸时应优先考虑酸度、盐度等工艺参数。     

两种吸附树脂对4B酸吸附行为的比较研究

研究了新型复合功能吸附树脂NDA-99和超高交联大孔吸附树脂JX-101对水溶液中4B酸(对甲苯胺-2-磺酸)的静态吸附行为和热力学特性，结果表明，NDA-99树脂对4B酸的吸附量明显大于JX-101树脂，两种树脂对4B酸的吸附均符合Freundlich吸附等温方程．其中，JX-101对4B酸的吸附属于物理吸附：NDA-99由于树脂表面存在弱碱性官能团，对4B酸的吸附表现为物理吸附和化学络合协同作用。     

大孔PNaA树脂对黄连素的吸附性能研究

将大孔D151树脂(聚丙烯酸树脂)用NaOH淋洗转化为大孔PNaA树脂(聚丙烯酸钠树脂),研究大孔PNaA树脂对黄连素的吸附性能。测定了PNaA树脂的持水量、弱碱交换量;比较PNaA树脂和X-5树脂、H103树脂、AB-8树脂、XAD-4树脂等吸附树脂对黄连素吸附量的大小;测定了PNaA树脂对黄连素在不同温度下的吸附等温线,利用热力学函数关系计算出了吸附焓、自由能和熵;测定了PNaA树脂对黄连素的吸附动力学;测定了PNaA树脂上黄连素在不同溶剂中的静态解吸率。实验表明:PNaA树脂对黄连素的吸附量明显大于X-5树脂、H103树脂、AB-8树脂、XAD-4树脂等吸附树脂对黄连素的吸附量;PNaA树脂对黄连素的吸附为放热、自发的过程;PNaA树脂对黄连素的吸附动力学数据符合一级吸附速率方程,颗粒内扩散是吸附速率的主要控制步骤,吸附动力学可采用HSDM模型加以描述;PNaA树脂上黄连素在0.1%NaCl和80%乙醇的混合溶液中静态解吸率为93.43%,解吸效果好。     

酚醛型吸附树脂对咖啡因和茶碱吸附性能的研究

用静态和动态方法研究了酚醛型吸附树脂JDW-2和DuoliteS-761对咖啡因和茶碱的吸附行为.结果表明,自制树脂JDW-2对咖啡因和茶碱的吸附性能明显优于DuoliteS-761.树脂的比表面积、含水量、酚羟基的含量与吸附关系密切,尽管JDW-2的比表面积比DuoliteS-761小,但前者比后者具有更高的含水量(42%)和酚羟基含量(3.72mmol/g).在静态条件下,JDW-2吸附咖啡因的速率比DuoliteS-761快,JDW-2树脂对咖啡因和茶碱饱和吸附量分别为246和127mg/g干树脂,而DuoliteS-761树脂对它们的吸附量分别为121和53mg/g干树脂;JDW-2和DuoliteS-761吸附咖啡因的初始阶段是粒扩散控制过程;酚醛型吸附树脂等温吸附咖啡因和茶碱的平衡吸附数据符合Langmuir方程.酚醛型吸附树脂吸附咖啡因和茶碱属单分子层吸附.在动态条件下,1mol/LHCl和40%甲醇溶液以1.5BV/h来洗脱吸附咖啡因的JDW-2,在4～5个床体积的洗脱率分别是88%和93%,而1mol/LHCl和80%甲醇溶液以1.5BV/h来洗脱吸附茶碱的JDW-2,在3～4个床体积的洗脱率分别是91%和96%,表明酚醛型吸附树脂具有良好的洗脱性能,用1mol/LHCl和40%(或80%)甲醇溶液作复合洗脱剂从JDW-2中洗脱咖啡因(或茶碱),效     

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.     

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.     

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.     

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.