改性聚乙烯膜和氧化硅固定化碳酸酐酶

doi:10.11949/0438-1157.20230348

摘要/Abstract

摘要：

分别以改性聚乙烯（PE）膜和氧化硅（SiO₂）为载体，考察了不同方法固定化碳酸酐酶（CA）的活性，然后以聚多巴胺/聚乙烯亚胺（PDA/PEI）改性的PE和SiO₂固定化CA为研究对象，考察了最适反应条件及稳定性。结果表明：在相同的反应条件下，PDA/PEI-SiO₂固定化CA的酶活回收率最高，为58.8%，PDA/PEI-PE固定化CA的酶活回收率为17.1%，使用10次后保留活性分别为84.8%和90.2%；固定化酶的最适反应条件均为35℃、pH 8.5，与游离酶相同；在较高温度（55~65℃）和较高酸浓度（>0.010 mol/L）下的稳定性高于游离酶；Mn²⁺对游离酶和固定化酶活性均有显著的促进作用，K⁺、Mg²⁺无明显影响；PDA/PEI-SiO₂和PDA/PEI-PE固定化CA在4℃下贮存10 d，保留活性分别为95.2%和92.4%；当用于CO₂水合反应时，CaCO₃的生成量分别是游离CA的120%和70%。固定化CA在CO₂捕集的工业化应用方面具有很大潜力。

关键词: 碳酸酐酶, 固定化, 聚乙烯, 氧化硅, 稳定性, 酶活

Abstract:

The activity of carbonic anhydrase (CA) immobilized by different methods was investigated using modified polyethylene (PE) membrane and silica (SiO₂) as carriers, and then modified with polydopamine/polyethyleneimine (PDA/PEI) PE- and SiO₂-immobilized CA were used as research objects. The optimum reaction conditions and stability were investigated. The results show that under the same reaction conditions, the activity recovery of PDA/PEI-SiO₂ immobilized CA was the highest, which was 58.8%, and the activity recovery of PDA/PEI-PE immobilized CA was 17.1%. Their retentive activities were 84.8% and 90.2%, respectively, after 10 use recycles. The optimum reaction conditions of immobilized enzymes were 35℃ and pH 8.5, which were the same as those of free enzymes. The stability of the two immobilized enzymes at higher temperature (55—65℃) and higher acid concentration (>0.010 mol/L) was better than that of free enzyme. Mg²⁺ could significantly promote the activity of free enzyme and immobilized enzyme, while K⁺ and Mg²⁺ had no obvious effect. PDA/PEI-SiO₂ and PDA/PEI-PE immobilized CA retained 95.2%和92.4% activity after stored at 4℃ for 10 d. When used in the CO₂ hydration reaction, the amount of CaCO₃ produced was 120% and 70% of free CA. The immobilized CA has great potential in the industrial application of CO₂ capture.

Key words: carbonic anhydrase, immobilization, polyethylene, silica, stability, enzyme activity

中图分类号:

TQ 814.2

孟令玎, 崇汝青, 孙菲雪, 孟子晖, 刘文芳. 改性聚乙烯膜和氧化硅固定化碳酸酐酶[J]. 化工学报, 2023, 74(8): 3472-3484.

Lingding MENG, Ruqing CHONG, Feixue SUN, Zihui MENG, Wenfang LIU. Immobilization of carbonic anhydrase on modified polyethylene membrane and silica[J]. CIESC Journal, 2023, 74(8): 3472-3484.

图/表 12

图1 CA在不同载体上的固定化路线

Fig.1 Immobilization routes of CA on different supports

图2 改性前后PE膜的SEM图

Fig.2 SEM images of PE films before and after modification

图3 改性前后SiO2的SEM图

Fig.3 SEM images of SO2 before and after modification

图4 载体改性前后的FTIR谱图

Fig.4 FTIR spectra of carriers before and after modification

表1 SiO2改性前后的表面Zeta电位

Table 1 Surface Zeta potential of SiO2 before and after modification

Samples	Zeta potential/mV
SiO₂	-51.5
PDA/PEI-SiO₂	+71.6
KH550-SiO₂	+20.5
KH560-SiO₂	-24.1

图5 不同载体和路线固定化CA的催化性能

Fig.5 Catalytic performance of CA immobilized by different carriers and different routes

图6 反应温度和pH对固定化CA活性的影响

Fig.6 Effects of reaction temperature and pH on the activity of immobilized CA

图7 固定化CA的热稳定性

Fig.7 Thermal stability of immobilized CA

图8 固定化CA的耐酸性

Fig.8 Acid resistance of immobilized CA

图9 固定化CA的离子稳定性

Fig.9 Ions stability of immobilized CA

图10 固定化CA的贮存稳定性

Fig.10 Storage stability of immobilized CA

表2 固定化CA的固碳性能

Table 2 CO2 sequestration performance of immobilized CA

Supports	$m C a C O 3$ /mg	m_CA/mg	( $m C a C O 3$ /m_CA)/ (mg/mg)	Ref.
Free CA	12.84	0.2	64.2	this work
PDA/PEI-SiO₂	15.68	0.2	78.4	this work
PDA/PEI-PE	9.33	0.2	46.6	this work
Mesoporous aluminosilicate	16.14	1	16.1	[51]
Alumino-siloxane aerogel beads	12	0.017	705.9	[52]
KH550-PVDF	~8	0.8	10.0	[13]
KH560-PVDF	~6	0.8	7.5	[13]

表2 固定化CA的固碳性能

Table 2 CO2 sequestration performance of immobilized CA

Supports	$m C a C O 3$ /mg	m_CA/mg	( $m C a C O 3$ /m_CA)/ (mg/mg)	Ref.
Free CA	12.84	0.2	64.2	this work
PDA/PEI-SiO₂	15.68	0.2	78.4	this work
PDA/PEI-PE	9.33	0.2	46.6	this work
Mesoporous aluminosilicate	16.14	1	16.1	[51]
Alumino-siloxane aerogel beads	12	0.017	705.9	[52]
KH550-PVDF	~8	0.8	10.0	[13]
KH560-PVDF	~6	0.8	7.5	[13]

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