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Chemisorption of CO2 by chitosan oligosaccharide/DMSO: organic carbamato–carbonato bond formation
Green Chemistry ( IF 9.8 ) Pub Date : 2017-08-15 00:00:00 , DOI: 10.1039/c7gc01830d
Abdussalam K. Qaroush 1, 2, 3, 4, 5 , Khaleel I. Assaf 6, 7, 8, 9 , Sanaa K. Bardaweel 3, 4, 5, 10, 11 , Ala'a Al-Khateeb 1, 5, 12, 13 , Fatima Alsoubani 1, 5, 12, 13 , Esraa Al-Ramahi 1, 5, 12, 13 , Mahmoud Masri 1, 9, 14, 15, 16 , Thomas Brück 1, 9, 14, 15, 16 , Carsten Troll 9, 15, 17, 18 , Bernhard Rieger 9, 15, 17, 18 , Ala'a F. Eftaiha 1, 5, 12, 13
Affiliation  

A newly formed bond of organic carbamato–carbonato emerged upon bubbling CO2 in a low molecular weight chitosan hydrochloride oligosaccharide CS·HCl/DMSO binary mixture. The aforementioned bond was detected and confirmed using attenuated total reflectance-Fourier transform Infrared (ATR-FTIR) spectroscopy, with two prominent peaks at 1551 cm−1 and 1709 cm−1 corresponding to ionic organic alkylcarbonate (RCO3) and carbamate (RNH–CO2 NH3+–R), respectively. 1H–, 13C–, and 1H–15N heteronuclear single quantum coherence (HSQC) NMR experiments were also employed. According to 13C NMR, two newly emerged peaks at 157.4 ppm and 161.5 ppm attributed for the carbonyl carbon within the sequestered species RCO3 and RNH–CO2 NH3+–R, respectively. Upon CO2 bubbling, cross peaks obtained from 1H–15N HSQC at 84.7 and 6.8 ppm correlated to the ammonium counterpart chemical shift bound to the proton resonances. Volumetric uptake of CO2 was measured using an ATR-FTIR autoclave equipped with a silicon probe. The equilibrium sorption capacity was 0.6 and 0.2 bars through the formation of RCO3 and RNH–CO2 NH3+–R, respectively. Moreover, physisorption by the dried DMSO contributed to additional 0.4 bars. Density functional theory (DFT) calculations supported the occurrence of the suggested dual mechanisms and confirmed the formation of carbonate at C-6 of the glucosamine co-monomer. Moreover, CS·HCl/DMSO showed a slight impact on cell proliferation after 48 hours; this was a clear evidence of its non-toxicity. The biodegradation test revealed that a degradation of about 80% of CS·HCl/DMSO was achieved after 33 days; these results indicated that this method is suitable for green industry. CS·HCl/DMSO showed modest activities against Staphylococcus aureus and Escherichia coli. In addition, CS·HCl/DMSO demonstrated a significant antifungal activity against Aspergillus flavus in comparison with Fluconazole.

中文翻译:

壳聚糖寡糖/ DMSO对CO 2的化学吸附:形成有机氨基甲酸酯-氨基甲酸酯键

当在低分子量壳聚糖盐酸盐低聚糖CS·HCl / DMSO二元混合物中鼓吹CO 2时,出现了一个新形成的有机氨基甲酸酯基-氨基甲酸酯键。检测上述键和证实使用衰减全反射傅立叶在1551厘米变换红外(ATR-FTIR)光谱,具有两个显着的峰-1和1709厘米-1对应于离子有机烷基碳酸酯基(RCO 3 - )和氨基甲酸酯(RNH –CO 2 - NH 3 + –R)。1 H–,13 C–和1 H– 15还使用了N个异核单量子相干(HSQC)NMR实验。根据13 C NMR,在157.4 ppm的和161.5 ppm的2个新出现的峰归因于所述隔离物种内的羰基碳RCO 3 -和RNH-CO 2 - NH 3 +分别-R。在CO 2鼓泡时,从1 H– 15 N HSQC在84.7和6.8 ppm处获得的交叉峰与结合到质子共振上的铵态化学位移相关。CO 2的体积吸收使用装备有硅探针的ATR-FTIR高压釜来测量。平衡吸附容量为0.6和0.2巴通过RCO的形成3 -和RNH-CO 2 - NH 3 + -R,分别。此外,干燥的DMSO的物理吸附贡献了另外的0.4 bar。密度泛函理论(DFT)计算支持所提出的双重机理的发生,并证实了C-6处碳酸盐的形成葡糖胺共聚单体。而且,CS·HCl / DMSO对48小时后的细胞增殖有轻微的影响。这是其无毒的明显证据。生物降解试验表明,经过33天的降解,CS·HCl / DMSO的降解率约为80%。这些结果表明该方法适用于绿色工业。CS·HCl / DMSO对金黄色葡萄球菌大肠杆菌的活性中等。另外,与氟康唑相比,CS·HCl / DMSO对黄曲霉表现出显着的抗真菌活性。
更新日期:2017-09-19
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