电子束辐照下克伦特罗的降解研究

克伦特罗是一种β2受体兴奋剂，是被欧美和我国农业部严格禁止的兽药。克伦特罗水溶液在电子束辐照下将发生降解。辐照计量不同，克伦特罗降解程度不同。采用质谱法测定克伦特罗溶液辐照前后的变化。当辐照计量大于6kGy时，克伦特罗降解率可达95％以上，说明这种辐照降解法具有一定的应用前景。     

预辐射聚丙烯反应挤出接枝丙烯酸的研究

利用电子束(EB)预辐照方法和反应挤出技术制备了聚丙烯接枝丙烯酸共聚物PP-g-AA. 采用化学滴定、红外光谱、偏光显微镜(PLM)、DSC和广角X射线衍射(WAXD)对接枝产物进行了表征. 研究结果表明, 接枝率随辐照剂量增加而增大并逐渐达到平台值, 但随单体浓度增大而表现为线性增加, 接枝链能起到异相成核作用, 从而提高了结晶速率并细化了球晶. 同时, 熔体流动速率(MFR)和力学性能测试结果表明, 预辐射和挤出过程造成了PP严重降解, 据此可认为接枝反应主要发生在聚丙烯断裂分子链的末端.     

电子束辐照与电化学还原联用技术——一种用于煤炭直接液化的新方法

对电子束辐照与电化学联用技术提高煤炭液化率的新型方法进行了研究。利用高能电子束对煤炭样品进行辐照,并通过四氢呋喃萃取出辐照后的可能产物并计算其提取率。实验结果发现,提取产率随着辐照剂量的增加而增加,并得到在氧气气氛下25 kGy的最佳辐照条件。辐照的样品进一步在氢氧化钠电解液中电化学还原液化,并采用元素分析法、傅里叶红外光谱法、阴极极化曲线法、核磁共振法和计时电流法等来检测辐照对煤炭电化学还原的影响。     

电子束辐照与电化学还原联用技术——一种用于煤炭直接液化的新方法(英文)

对电子束辐照与电化学联用技术提高煤炭液化率的新型方法进行了研究。利用高能电子束对煤炭样品进行辐照,并通过四氢呋喃萃取出辐照后的可能产物并计算其提取率。实验结果发现,提取产率随着辐照剂量的增加而增加,并得到在氧气气氛下25 kGy的最佳辐照条件。辐照的样品进一步在氢氧化钠电解液中电化学还原液化,并采用元素分析法、傅里叶红外光谱法、阴极极化曲线法、核磁共振法和计时电流法等来检测辐照对煤炭电化学还原的影响。     

γ-g-辐照-O3氧化联合作用下4-氯酚的降解

研究了⁶⁰Co γ-射线辐照以及辐照-臭氧氧化联合作用下4-氯酚的降解情况. 通过总有机碳(TOC)分析, 研究了γ辐照对反应体系中4-氯酚的无机化程度及无机化过程的动力学特征, 同时还探讨了初始浓度以及自由基清除剂对4-氯酚降解效果的影响. 实验结果表明: 当辐照剂量率为336 Gy·min^-1时, 2 kGy的辐照剂量可以使10 mg·L^-1 的4-氯酚完成降解. 辐照-O₃联合作用时氯酚的降解速率常数最大, 为0.1016 min^-1, 相当于单独辐照(0.0294 min^-1)与单独O3氧化(0.0137 min^-1)时的降解速率常数之和的2.4倍. 这表明4-氯酚的辐照降解机理以自由基氧化为主, 与单独采用辐照处理相比, 辐照-O₃氧化联合作用对水溶液中4-氯酚的脱氯和彻底降解具有协同效应.     

可重复使用的有序介孔碳-氧化钛吸附-光催化剂用于去除水中苯酚

制备了有序介孔碳-氧化钛吸附-光催化剂,利用可见光高效降解水中苯酚.为去除水中高浓度苯酚,设计了吸附-光催化循环,即暗条件吸附8h,分离催化剂和将固体催化剂置于可见光下辐照8h.经过10次循环,水中高浓度苯酚(200mg/L)几乎可被完全降解.详细讨论了TiO₂晶格中非金属掺杂、介孔碳壁对TiO₂纳米颗粒聚集的阻抑作用、介孔孔道吸附苯酚性能等因素对吸附-光催化剂性能的影响.有序介孔碳-氧化钛复合体有效地结合了物理吸附和光化学降解技术,有望用于降解水中难生物降解的高浓度有机污染物.     

聚乙烯导热复合材料的电子束辐照改性

将低密度聚乙烯(LDPE)、氧化铝(Al₂O₃)和纳米二氧化硅(SiO₂)进行熔融共混,再通过电子束辐照对得到的材料进行改性,得到了同时具有高导热性能和力学性能的复合材料(PE-Al-Si)。 当纳米SiO₂的质量分数为1%,电子束辐照剂量为120 kGy时,与不含SiO₂的复合材料(PE-Al)相比,PE-Al-Si的导热系数达到了0.759 W/(m·K),提高了22%。 另外,PE-Al-Si的拉伸强度比PE-Al提高了17%。 证明SiO₂不仅可以改善复合材料的力学性能,同时还提高了辐照效率及复合材料的导热性能。     

负载型贵金属纳米粒子作为光/超声催化剂在化学合成和降解污染物方面的应用

综述了Au/TiO2、Au/ZrO2、Ag/AgCl等负载型贵金属纳米粒子作为有效的光/超声催化剂在化学合成和降解污染物方面的应用.负载型贵金属纳米粒子能够有效地将太阳能转化为化学能.在紫外光或可见光的辐照下,负载型贵金属纳米粒子能够催化一系列的选择性化学转化,如醇类化合物氧化为醛/酮类化合物、硫醇氧化为二硫化合物、苯氧化为苯酚、硝基苯类化合物还原为偶氮化合物等.在超声波辐射下,负载型贵金属纳米粒子能够有效地催化分解水产氢.此外,在紫外光或可见光的辐照下,负载型贵金属纳米粒子能够有效地催化降解多种污染物,如醛类、醇类、酸类、酚类化合物和染料等.在超声波辐射下,负载型贵金属纳米粒子也能够有效地催化降解包括染料在内的有机污染物.     

壳聚糖在水溶液中的辐射降解反应

研究了壳聚糖在CH3COOH/NaCl缓冲溶液均相体系下的辐射降解反应,给出了H2O2、异丙醇、pH、样品初始分子量等因素对壳聚糖降解的影响,探讨了实验条件下溶液中不同自由基对壳聚糖降解的作用,并对辐照前后壳聚糖的结构进行了表征.结果表明,酸性条件下,壳聚糖的降解主要由.H和.OH自由基共同作用引起,加入H2O2或者通入N2O都能够略微提高.OH自由基浓度,对壳聚糖的降解有促进作用.加入异丙醇后,由于同时降低了.H和.OH自由基浓度,导致壳聚糖降解缓慢.当溶液的pH接近中性后,对壳聚糖的降解起主要作用的为.OH自由基,加入H2O2或者通入N2O都会增加.OH自由基的浓度,从而明显提高壳聚糖的降解速率.此外,研究发现低分子量的壳聚糖具有较快的降解速率.样品的UV、FTIR分析表明,辐照后除在壳聚糖分子链端生成羰基外,壳聚糖主链结构未见变化,脱乙酰度也没有显著改变,显示出辐射降解是一种有效的控制壳聚糖分子量方法.     

大剂量范围电子束辐照超高分子量聚乙烯纤维结构与性能研究

采用高能电子束辐照方法获得了一系列从20kGy到1000kGy大剂量辐照范围的超高分子量聚乙烯纤维(UHMWPE fiber)。通过凝胶含量测试和溶胶流变性能测试定性和定量表征了辐照过程的交联和裂解效应,利用差示扫描量热仪(DSC)和X射线衍射仪(XRD)表征了辐照产物的结晶性能,并且利用热机械分析仪(TMA)表征了辐照纤维在高温恒温条件下的热尺寸稳定性。结果表明,高能电子束辐照对于UHMWPE纤维具有交联和裂解两种作用;大剂量辐照下会造成纤维熔点和熔融热焓降低,法线方向晶粒平均尺寸有明显变小;辐照交联大大提高了纤维的热尺寸稳定性。     

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.     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.