We described a novel polymer-lipase conjugate for high-efficient esterification of vitamin E using vitamin E and succinic anhydride as the substrates in nonaqueous media.In this work,the monomer,N-isopropylacrylamide(...We described a novel polymer-lipase conjugate for high-efficient esterification of vitamin E using vitamin E and succinic anhydride as the substrates in nonaqueous media.In this work,the monomer,N-isopropylacrylamide(NIPAM),was grafted onto Candida rugosa lipase(CRL)to synthesize poly(NIPAM)(pNIPAM)-CRL conjugate by atom transfer radical polymerization via the initiator coupled on the surface of CRL.The result showed that the catalytic efficiencies of pNIPAM-CRL conjugates(19.5-30.3 L·s^(-1)·mmol^(-1))were at least 7 times higher than that of free CRL(2.36 L·s^(-1)·mmol^(-1))in DMSO.It was attributed to a significant increase in Kcat of the conjugates in nonaqueous media.The synthesis catalyzed by pNIPAM-CRL co njugates was influenced by the length and density of the grafted polymer,water content,solvent polarity and molar ratio of the substrates.In the optimal synthesis,the reaction time was shortened at least 7 times,and yields of vitamin E succinate by pNIPAM-g-CRL and free CRL were obtained to be 75.4%and 6.6%at 55℃after the reaction for 1.5 h.The result argued that conjugation with pNIPAM induced conformational change of the lid on CRL based on hydrophobic interaction,thus providing a higher possibility of catalysis-favorable conformation on CRL in nonaqueous media.Moreover,pNIPAM conjugation improved the thermal stability of CRL greatly,and the stability improved further with an increase of chain length of pNIPAM.At the optimal reaction conditions(55℃and 1.5 h),pNIPAM-g-CRL also exhibited good reusability in the enzymatic synthesis of vitamin E succinate and kept~70%of its catalytic activity after ten consecutive cycles.The research demonstrated that pNIPAM-g-CRL was a more competitive biocatalyst in the enzymatic synthesis of vitamin E succinate and exhibited good application potential under harsh industrial conditions.展开更多
The large system analysis(LSA)has recently been shown to be a very useful tool for computing the average achievable rate.In this paper,we use LSA to derive the users’average achievable rate of multi-antenna two-way r...The large system analysis(LSA)has recently been shown to be a very useful tool for computing the average achievable rate.In this paper,we use LSA to derive the users’average achievable rate of multi-antenna two-way relay networks with interference alignment(IA),and we then derive the rate expressions under both equal power allocation and optimal power allocation.It is shown that the obtained closed-form rate expressions are functions of the average signal-to-noise ratio(SNR)for each data stream.Extensive simulation studies show that the average achievable rate expressions derived through LSA provide accurate estimates of the average achievable rate for two-way relay networks with interference alignment.展开更多
基金financially supported by the National Key Research and Development Program of China (2021YFC2102801)National Natural Science Foundation of China (21878221)+1 种基金the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (21621004)the Haihe Laboratory of Sustainable Chemical Transformations for financial support.
文摘We described a novel polymer-lipase conjugate for high-efficient esterification of vitamin E using vitamin E and succinic anhydride as the substrates in nonaqueous media.In this work,the monomer,N-isopropylacrylamide(NIPAM),was grafted onto Candida rugosa lipase(CRL)to synthesize poly(NIPAM)(pNIPAM)-CRL conjugate by atom transfer radical polymerization via the initiator coupled on the surface of CRL.The result showed that the catalytic efficiencies of pNIPAM-CRL conjugates(19.5-30.3 L·s^(-1)·mmol^(-1))were at least 7 times higher than that of free CRL(2.36 L·s^(-1)·mmol^(-1))in DMSO.It was attributed to a significant increase in Kcat of the conjugates in nonaqueous media.The synthesis catalyzed by pNIPAM-CRL co njugates was influenced by the length and density of the grafted polymer,water content,solvent polarity and molar ratio of the substrates.In the optimal synthesis,the reaction time was shortened at least 7 times,and yields of vitamin E succinate by pNIPAM-g-CRL and free CRL were obtained to be 75.4%and 6.6%at 55℃after the reaction for 1.5 h.The result argued that conjugation with pNIPAM induced conformational change of the lid on CRL based on hydrophobic interaction,thus providing a higher possibility of catalysis-favorable conformation on CRL in nonaqueous media.Moreover,pNIPAM conjugation improved the thermal stability of CRL greatly,and the stability improved further with an increase of chain length of pNIPAM.At the optimal reaction conditions(55℃and 1.5 h),pNIPAM-g-CRL also exhibited good reusability in the enzymatic synthesis of vitamin E succinate and kept~70%of its catalytic activity after ten consecutive cycles.The research demonstrated that pNIPAM-g-CRL was a more competitive biocatalyst in the enzymatic synthesis of vitamin E succinate and exhibited good application potential under harsh industrial conditions.
基金supported by the National Natural Science Foundation of China(61671253,61971241,61631020 and 91738201)the Major Projects of the Natural Science Foundation of the Jiangsu Higher Education Institutions(16KJA510004)+1 种基金the Natural Science Foundation of Jiangsu Province(Grant Nos.BK20171446)the open research fund of National and Local Joint Engineering Laboratory of RF Integration and Micro-Assembly Technology of Nanjing University of Posts and Telecommunications(KFJJ20170305)。
文摘The large system analysis(LSA)has recently been shown to be a very useful tool for computing the average achievable rate.In this paper,we use LSA to derive the users’average achievable rate of multi-antenna two-way relay networks with interference alignment(IA),and we then derive the rate expressions under both equal power allocation and optimal power allocation.It is shown that the obtained closed-form rate expressions are functions of the average signal-to-noise ratio(SNR)for each data stream.Extensive simulation studies show that the average achievable rate expressions derived through LSA provide accurate estimates of the average achievable rate for two-way relay networks with interference alignment.
