双变性淀粉吸附剂的合成及吸附性能研究

以环氧氯丙烷、交联化淀粉和丙烯腈为原料,水为溶剂,硝酸铈铵为引发剂,通过接枝反应合成了双变性淀粉吸附剂。其最佳制备工艺条件是交联化淀粉2g,硝酸铈铵浓度0.004mol/L,丙烯腈浓度0.3774mol/L,接枝温度35℃,接枝时间240min,料液比1:10(W/V)。对制得的双变性淀粉进行金属离子吸附性能评价,发现Cr6 吸附时使溶液处于中性或微酸性环境下,Cu2 吸附时使溶液处于弱碱性环境下,Cu2 的吸附率达到86.3%,Cr6 吸附率达78.2%,Cu2 吸附效果大于Cr6 。     

天然水中优势菌胞外聚合物及其中主要成分对铅的吸附

研究了吉林省长春市南湖天然水环境中生物膜胞外聚合物及由其分离得到的胞外多糖和胞外蛋白对铅的吸附特性,讨论了时间、pH值、其它共存金属离子等对其吸附的影响;初步探讨了胞外多糖和胞外蛋白吸附铅的反应机理. 结果表明,3种吸附剂对铅的吸附量在pH=6时最大,分别为23.64、15.8和3.48 mg/g ;吸附体系均在6h以后达到吸附平衡;共存金属离子镉对铅的吸附有影响.胞外聚合物及其中的胞外多糖和胞外蛋白对铅的吸附过程符合Langmuir和Freundlich热力学方程.胞外聚合物中胞外多糖对铅的吸附所作贡献大于胞外蛋白.胞外蛋白的胺基、酰胺基,胞外多糖的羟基、酰胺基等是胞外聚合物吸附铅离子过程中起关键作用的化学基团.     

天然水优势菌胞外聚合物及主要成分对cd2+的吸附特征

利用原子吸收法,研究了长春市南湖天然水环境中生物膜优势菌种的胞外聚合物及其主要成分胞外多糖和胞外蛋白对Cd2 的吸附特性,讨论了时间、pH值、其它共存金属离子等对其吸附反应的影响。利用红外光谱分析法对吸附反应机理进行了初步探讨。结果表明,胞外聚合物、胞外多糖和胞外蛋白对Cd2 的吸附均在pH=6时吸附量最大;对Cd2 的吸附均在6 h以后达到平衡;共存金属离子如Pb2 对Cd2 的吸附有干扰。对Cd2 的吸附过程符合Langmu ir和Freund lich热力学方程。3种吸附剂对Cd2 的吸附能力为:胞外聚合物>胞外多糖>胞外蛋白。胞外蛋白的胺基、酰胺基,胞外多糖的羟基、酰胺基等在吸附Cd2 过程中是起关键作用的化学基团。     

嗜铅菌对水中重金属Pb~(2+)的吸附研究

研究了实验室提供的嗜铅菌对水中铅离子吸附的条件和机理.讨论了吸附时间、pH、铅离子的质量浓度和菌的质量浓度对吸附的影响.结果表明,在pH=7.0、铅离子初始质量浓度为25mg/L、离心湿菌的质量浓度为1.06g/L、吸附时间为60min时,铅离子的吸附率达96.88%;实验条件下超标25倍的含Pb~(2+)废水,可迭排放标准;Pb~(2+)的最大吸附量为150mg/g.数学模型Langmuir和Freundlich方程均能很好地描述嗜铅菌对Pb~(2+)的吸附过程.对Pb~(2+)吸附前后的红外光谱表征表明,嗜铅菌表面多糖、蛋白质的羟基峰和羰基峰均有不同程度的紫移,羟基峰、糖苷峰等峰宽略增,说明菌体吸附,主要是表面基团的作用所致.用原子力显微镜对吸附前后的嗜铅菌检测可见,吸附后菌体的弹性变小、粘性变大、部分茵体有一定的收缩,说明以表面吸附为主的吸附过程,对菌细胞的聚合度有影响,菌体内部对铅也有一定的生物积累.     

交联化羟丙基壳聚糖对Cr(Ⅵ)的吸附与结构分析

研究了交联化羟丙基壳聚糖对Cr(Ⅵ)的吸附作用,探讨了溶液的pH值、反应时间、温度、初始浓度等因素对其吸附性能的影响,并且用FTIR、XRD和SEM对吸附前后物质进行了表征与结构分析。实验表明,pH是交联羟丙基壳聚糖吸附Cr(Ⅵ)的主要影响因素。在pH=5时,对Cr(Ⅵ)初始浓度为15mg/L的溶液,可控制温度在20℃左右吸附2h,吸附剂交联羟丙基壳聚糖用量为1g/100mL溶液即能达到满意的吸附效果。吸附后由于交联羟丙基壳聚糖与Cr(Ⅵ)的配位作用使得交联羟丙基壳聚糖的结晶性明显降低;Cr(Ⅵ)的配位使得交联羟丙基壳聚糖的表面形貌发生了改变。     

含硫液体烃燃料水蒸气重整制氢 Ⅱ. Pt/Ce_(0.8)Gd_(0.2)O_(1.9)催化剂的原位DRIFTS表征

利用原位红外漫反射技术(DRIFTS)对抗硫中毒催化剂Pt/Ce0.8Gd0.2O1.9(Pt/CGO)上CO吸附、CO/噻吩共吸附以及CO/H2S顺序吸附进行了研究,并与Pt/Al2O3催化剂进行了比较.CO吸附实验表明,1.6%Pt/CGO-800(800℃焙烧)上CO的红外特征吸收峰在2104cm-1,与1.6%Pt/Al2O3-500上CO的红外特征吸收峰(2070cm-1)相比,向高波数方向移动了34cm-1.1.6%Pt/CGO-600上出现两个CO特征吸收峰,主峰位于2108cm-1,肩峰位于2085cm-1.CO/噻吩共吸附实验表明,噻吩导致1.6%Pt/CGO-800上CO吸附的红外特征吸收峰红移至2090cm-1,峰强度略有降低;1.6%Pt/CGO-600上CO的红外特征吸收峰红移至2096cm-1且强度有所降低,同时肩峰消失.而1.6%Pt/Al2O3-500上CO的红外特征吸收峰明显减弱并红移至2040cm-1.CO/H2S顺序吸附实验表明,H2S导致Pt/CGO催化剂在2104和2108cm-1处的CO特征吸收峰轻微红移,峰强度略有降低,而H2S导致Pt/Al2O3完全丧失CO的吸附能力.原位DRIFTS表征结果表明,Pt/CGO催化剂上生成的强缺电子特性Pt颗粒具有很强的抗硫中毒能力,800℃焙烧有利于生成单一的抗硫中毒的强缺电子Pt金属位,使得1.6%Pt/CGO-800具有最佳的抗硫中毒性能.     

β-环糊精聚合物包结PAN树脂富集-XRF测定痕量Cu,Co,Cr与Pb

采用自行合成的β-环糊精交联聚合物包结PAN螯合树脂,研究了该树脂对部分重金属元素的吸附性能。并利用XRF适合固体试样、多元素同时测定的特点,将试样中多种重金属元素富集后过滤制成薄样,不经洗脱直接采用XRF进行测定。建立了XRF测定痕量Cu、Co,Cr和Pb的新方法。方法可应用于环境水样中痕量Cu,Co,Cr与Pb的测定。     

含硫液体烃燃料水蒸气重整制氢II. Pt/Ce0.8Gd0.2O1.9 催化剂的原位DRIFTS表征

利用原位红外漫反射技术(DRIFTS)对抗硫中毒催化剂Pt/Ce0.8Gd0.2 O1.9(Pt/CGO)上CO吸附、CO/噻吩共吸附以及CO/H2S顺序吸附进行了研究,并与 Pt/Al2O3催化剂进行了比较. CO吸附实验表明, 1.6%Pt/CGO-800(800 ℃焙烧)上CO的红外特征吸收峰在 2 104 cm-1, 与1.6%Pt/Al2O3-500上CO的红外特征吸收峰(2 070 cm-1)相比,向高波数方向移动了34 cm-1. 1.6%Pt/CGO-600上出现两个CO特征吸收峰,主峰位于 2 108 cm-1, 肩峰位于 2 085 cm-1. C O/噻吩共吸附实验表明,噻吩导致1.6%Pt/CGO-800上CO吸附的红外特征吸收峰红移至 2 090 cm-1, 峰强度略有降低;1.6%Pt/CGO-600上CO的红外特征吸收峰红移至 2 096 cm -1 且强度有所降低,同时肩峰消失. 而1.6%Pt/Al2O3-500上CO的红外特征吸收峰明显减弱并红移至 2 040 cm-1. CO/H2S顺序吸附实验表明, H2S导致Pt/CGO 催化剂在 2 104 和 2 108 cm-1 处的CO特征吸收峰轻微红移,峰强度略有降低,而H2S导致Pt/Al2O3完全丧失CO的吸附能力. 原位DRI FTS表征结果表明, Pt/CGO催化剂上生成的强缺电子特性Pt颗粒具有很强的抗硫中毒能力, 8 00 ℃焙烧有利于生成单一的抗硫中毒的强缺电子Pt金属位,使得1.6%Pt/CGO-800具有最佳的抗硫中毒性能.     

硅胶表面铜离子印迹聚合物的制备和性能研究

以Cu2+为模板,1,4-二羟基蒽醌为单体,硅胶为载体,γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH-570)为偶联剂,利用表面离子印迹技术制备了Cu2+印迹聚合物。采用紫外光谱法、傅里叶变换红外光谱法(FT-IR)、扫描电镜对Cu2+印迹聚合物进行结构和表面形貌表征,并用原子吸收光谱法考察了吸附时间、吸附酸度、吸附温度、吸附浓度等对聚合物吸附性能的影响,研究了印迹聚合物在混合溶液中对Cu2+的选择性,将该聚合物重复利用6次,吸附量达到第一次的82%,并将该印迹聚合物应用到河水和自来水中,能够有效地测出水中铜离子的浓度,回收率分别为95.5%和107.2%。     

含氮杂冠醚双亲聚合物纳米球的制备及性能

设计、合成了含氮杂冠醚和腺嘌呤的双亲聚合物,聚[N,N-二乙氧基-1,10-二氮杂-18冠-6-5-甲基-腺嘌呤-异酞酸酯](PCASE).SEM观测到在水溶液中该聚合物与5-氟尿嘧啶(5-flu)小分子识别后自发聚集成直径约140～210nm的纳米球,用动态光散射测得水溶液中PCASE/5-flu纳米球的粒径主要集中在120～230nm范围内,FTIR研究了PCASE/5-flu纳米球内聚合物PCASE中腺嘌呤与底物5-氟尿嘧啶的分子识别,结果表明,识别后5-氟尿嘧啶环上C(2)=O伸缩振动峰从1724cm-1位移至1718cm-1,且聚合物中腺嘌呤NH2峰3324cm-1消失,出现了一个新的NH2峰3432cm-1,说明5-氟尿嘧啶环上C(2)=O与聚合物PCASE中腺嘌呤上NH2间形成了氢键.变温红外谱显示,识别后的羰基峰1718cm-1随温度的升高逐渐向高波数回移,并最终稳定在5-氟尿嘧啶环上C(2)=O识别前的1724cm-1处,且识别后产生的新NH2峰3432cm-1随温度的升高逐渐减弱至消失,表明所形成的氢键断裂.     

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.     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.