胍盐键合型聚氨酯涂料的制备及其抗菌防霉性能

采用化学键合的方式将聚六亚甲基盐酸胍(PHMG)键合到聚氨酯(PU)分子链上,制得抗菌PU涂料PU-PHMG。利用红外光谱(FT-IR)、阿贝折射仪、原子力显微镜(AFM)等对其结构与性能进行了表征,用振荡法、抑菌圈法等对其抗菌性能进行了测试,同时探究了PHMG的质量分数对PU涂料各项性能的影响。研究表明:当PHMG的质量分数为1.0%时,PHMG的键合效率达到93.59%,对大肠杆菌和金黄色葡萄球菌的抑菌率达到99.5%以上,证明PU-PHMG具有优异持久的抗菌性能。此外,该涂料还兼具优异的防霉性能和力学性能。     

化学键合法制备长效抗菌聚对苯二甲酸乙二醇酯材料及其性能

通过化学反应将抗菌剂聚六亚甲基盐酸胍(PHMG)键合到聚对苯二甲酸乙二醇酯(PET)基体上,制得抗菌剂质量分数为15%的PET抗菌母料(PET-g-PHMG),PHMG与PET的键合效率达93.7%.透射电子显微镜(TEM)结果表明,化学键的键合作用提高了PHMG与PET的相容性,使得极性的PHMG以纳米尺寸均匀分布在PET-g-PHMG中.在PET基体中添加少量PET-g-PHMG,可制成不同抗菌剂含量的PET样品,抗菌母料PET-g-PHMG的添加可抑制PET基体的降解,提高抗菌PET样品的特性黏度.所得抗菌PET样品对大肠杆菌和金黄色葡萄球菌的抑菌率均在99%以上,即使反复水洗,抗菌性能也无明显降低.该抗菌PET样品具有良好的可纺性,通过熔融纺丝可以制成抗菌PET纤维,其抗菌性能具有耐水洗性,抗菌动力学测试结果表明,该抗菌PET样品对革兰氏阴性和阳性细菌还具有较快速的杀灭作用.     

抗菌水凝胶敷料的制备及性能

以乙二醇二缩水甘油醚(GDE)为偶联剂,将胍盐低聚物(PHMG)接枝到淀粉上,形成淀粉接枝物(Starch-g-PHMG)。然后,将一定比例的Starch-g-PHMG与淀粉-丙烯酸接枝共聚物共混,制备了抗菌水凝胶敷料(AHD)。通过红外光谱(FT-IR)、元素分析确定了Starch-g-PHMG的分子结构;通过吸液测试、抗菌测试表征了AHD的理化性能。结果表明:在反应温度为60°C,反应时间为3h,w(NaOH)=0.4%时,Starch-g-PHMG中PHMG的接枝效率最高,可达37.5%;AHD的吸液率随着Starch-g-PHMG含量的增加而减少;当w(PHMG)0.33%时,AHD对金黄色葡萄球菌与大肠杆菌的抑菌率可以达到100%。     

抗菌淀粉-聚乙烯醇水凝胶的制备及性能

以环氧氯丙烷为键合剂将胍盐低聚物（PHMG）接枝到淀粉分子上,设计了正交试验优化接枝反应条件。将产物添加到淀粉和聚乙烯醇（PVA）水溶液中,采用化学交联法合成了具有抗菌性能的淀粉-聚乙烯醇（S-PVA）水凝胶,测试了水凝胶的溶胀率、脱水率以及抗菌性能。结果表明：当反应温度为40°C、时间为0.5 h、pH为9时,PHM...     

键合胍盐低聚物的抗菌聚苯乙烯的制备及其抗菌活性

在Haake转矩流变仪中,将盐酸胍与己二胺的低聚物(PHMG)与末端带环氧基的遥爪型聚苯乙烯(PS)进行熔融反应,得到具有抗菌性能的聚苯乙烯(PS-PHMG)。红外(FT-IR)光谱证明胍盐低聚物是以化学键的形式键合到PS分子链上的。分别用扩散法和振荡瓶法测试了抗菌聚苯乙烯对大肠杆菌和金黄色葡萄球菌的抗菌性能。扩散法实验表明,经提纯后的PS-PHMG不存在胍盐低聚物的溶出,但对大肠杆菌和金黄色葡萄球菌均有明显的抑菌圈。振荡瓶法结果表明:当PS中w(PS-PHMG)=0.2%(即w(PHMG)=0.069%)时,与大肠杆菌接触30 mi m后,抑菌率达100%;当w(PS-PHMG)=0.1%(即w(PHMG)=0.035%)时,30 min内对金黄色葡萄球菌的抑菌率也能够达到100%,具有较好的抗菌速效性,杀灭细菌的时间小于30 min。     

胍盐低聚物及其在聚丙烯中的热稳定性分析

将自制的胍盐低聚物(PHMG)分别以熔融共混和键合反应的方式引入到聚丙烯(PP)基体中.用透射电子显微镜(TEM)观察了两种不同引入方式下 PHMG 在 PP 基体中的分布,并用热重分析法(TGA)研究了它们的热分解特性.研究表明:PHMG 与 PP 的熔融共混由于两者之间极性相差较大,PHMG 倾向于以团簇的形式分布在 PP 基体中,分布不均匀,其共混物倾向于按PHMG、PP 各自的规律降解;但 PHMG 与 PP 进行键合后,PHMG 则均匀分布在 PP 基体中,PHMG 倾向于与 PP 同时降解.     

季铵盐接触型水性聚氨酯的制备及其抗菌性能

以叔胺化合物3-二甲胺基-1,2-丙二醇为扩链剂、甲基丙烯酸羟乙酯（HEMA）为封端剂,将叔胺基团、不饱和基团键合到聚氨酯（PU）分子链上,并采用不同烷基链长卤代烷与叔胺基团发生季铵化反应引入亲水性基团,经紫外光固化,制备了水性聚氨酯（WPU）抗菌薄膜。利用红外光谱仪、纳米粒度分析仪、光学接触测试仪等对WPU分散液及其薄膜的结构与性能进行表征,通过震荡摇瓶、抑菌圈进行抗菌性能测试,并探究了叔胺化合物对材料性能的影响。结果表明：当叔胺化合物质量分数为9%、烷基链长为12时,WPU通过接触分别对大肠杆菌、金黄色葡萄球菌的抗菌率达99.5%以上,并表现出优异的抗菌持久性能。此外,所制备的水性聚氨酯材料还具有良好的力学性能。     

键合聚六亚甲基胍盐酸盐的聚丙烯蜡的制备及其抗菌活性

在Hakke转矩流变仪中,将聚丙烯蜡（PPw）接枝马来酸酐（PPW—g—MAH）与聚六亚甲基胍盐酸盐（PHMG）熔融反应,得到具有抗茵性能的聚丙烯蜡（PPW—g—PHMG）。透射电镜显示PHMG在PPw一舻PHMG上呈纳米尺度均匀分布。将聚丙烯与PPW—g—PHMG混合,混和物（PP／PPw—g—PHMG）的抑茵圈法和贴膜法抗茵性能测试结果显示：样品对大肠杆菌具有优异的抗菌性能。经过提纯后,PP／PPw—g—PHMG没有出现PHMG的溶出,具有非溶出性的、持久的抗茵功能。     

Bis-GMA复合牙科材料的合成和抗菌改性

以甲基丙烯酸缩水甘油酯（GMA）修饰聚六亚甲基胍盐酸盐（PHMG）,制备端基具有甲基丙烯酸酯基的抗菌改性剂PHMG-GMA。将PHMG-GMA与树脂双酚A-甲基丙烯酸缩水甘油酯（Bis-GMA）、稀释剂二甲基丙烯酸二缩三乙二醇酯（TEGDMA）、填料纳米SiO2、光引发剂樟脑醌（CQ）混合均匀,经紫外灯固化后得到了具有抗菌性能的复合牙科材料。测试了该材料的抗菌性能,研究了SiO2、PHMG-GMA的加入对紫外透过率的影响。结果表明：随着SiO2含量的增加,材料的紫外透过率下降。当PHMG-GMA的质量分数为1.0%时,复合牙科材料对变形链球菌的抑菌率达到99.99%。     

键合喹诺酮类药效基团的抗菌聚丙烯酰胺的制备及其抗菌性能

设计合成了两种含喹诺酮类药效基团的新型甲基丙烯酸酯单体,分别将其与丙烯酰胺通过自由基共聚合成了两种共聚物。采用1 H-NMR、13C-NMR、GPC和分光光度计等手段对大单体和共聚物的结构进行了表征。分别测定了这两种甲基丙烯酸酯单体和共聚物对大肠杆菌和金黄色葡萄球菌的最低抑菌浓度(MIC)。结果表明:这两种共聚物均具有高效的抗菌性能,并且键合环丙沙星的聚丙烯酰胺的抗菌能力明显优于键合吡哌酸的聚丙烯酰胺。     

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%.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.