固定化脲素酶的活化载体制备的方法

酶是参与机体多种化学反应的生物催化剂。在近代生物化学的发展中,酶的应用更加广泛,但酶对热、强酸、强碱、有机溶媒不稳定,很快失活。近年来通过载体活化制备固定化酶,它具有酶特有的催化活性,不溶于水和高的稳定性。因此在研究酶的利用,特别是制作生物化学传染器上是非常有利的。本实验是以光谱纯SiO_2颗粒及含SiO_260%的玻璃纤维膜作为固定脲素酶载体。采用氨基硅烷化和戊二醛交联的方法制备了固定脲素酶的活化载体。经固定化效果检验。

硅胶负载型聚烯烃催化剂(Ⅰ)──不同类型硅胶载体热活化颗粒的TEM和SAED研究

利用TEM和选区电子衍射（SAED）方法对T-1，T-3和T-4三种硅胶载体原料及其受热活化过程的影响进行了研究，阐明了各种硅胶载体颗粒中原级粒子的尺度、形态和结合特征，以及它们受不同热活化条件的影响。并发现了600℃热活化使T-3和T-4硅胶载体颗粒发生局部烧结现象的实验依据。

硅胶负载型聚烯烃催化剂(Ⅱ)──热活化硅胶载体及催化剂颗粒的TEM和SAED研究

利用TEM和选区电子衍射（SAED）的方法对T-1硅胶载体颗粒在800℃和900℃热活化条件下的变化进行了研究，阐明了硅胶载体颗粒中原级粒子的尺度、形态和结合特征等受热活化条件的影响。并发现了T-1硅胶载体颗粒发生局部烧结现象起始温度为900℃的实验依据。对催化剂颗粒的研究表明，在一定的催化剂组分配比条件下，组分的负载化对热活化载体颗粒的结构形态影响很小，催化剂的物相结构特征不会改变。

乙二胺羟丙基壳聚糖固定化天门冬酰胺酶的研究

研制了新型壳聚糖胺基衍生物——乙二胺羟丙基壳聚糖 ( EDA- HPCS) ,并将其用于固定天门冬酰胺酶。分别考察了甲醛活化载体和戊二醛活化载体对固定化酶活力的影响。结果表明 ,在适当的固定化条件下 ,甲醛活化 EDA- HPCS的固定化酶活力约为 30 U/g载体 ,而戊二醛活化EDA- HPCS固定化酶活力约为 1

酶传感器中GOD酶固定化方法条件的选择

目的 研究尼龙网上胆碱氧化酶的不同固定化方法对酶活性的影响 ,以及测定体系pH值的选择。方法 采用活化载体 共价结合法和戊二醛交联法。结果 发现用改进后的活化载体 共价结合法固定的酶活性高 ,使用寿命长 ,酶不易损失 ,重现性好。

A palladium single-atom catalyst toward efficient activation of molecular oxygen for cinnamyl alcohol oxidation

Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging,with the activation of molecular oxygen(O2)as a crucial capability of the catalysts.Herein,we demonstrate that an Al2O3-supported Pd single-atom catalyst leads to higher activity and selectivity compared to Pd nanoparticles for the oxidation of cinnamyl alcohol.The Al2O3 support used in this study is rich in coordinately unsaturated Al3+sites,which are apt for binding to Pd atoms through oxygen bridges and present a distinct metal-support interaction(MSI).The suitable MSI then leads to a unique electronic characteristic of the Pd single atoms,which can be confirmed via X-ray photoelectron spectroscopy,normalized X-ray absorption near-edge structure,and diffuse reflectance Fourier transform infrared spectroscopy.Moreover,this unique electronic state is proposed to be responsible for its high catalytic activity.With the help of in-situ UV-vis spectra and electron spin resonance spectra,a specific alcohol oxidation route with O2 activation mechanism is then identified.Active oxygen species behaving chemically like singlet-O2 are generated from the interaction of O2 with Pd1/Al2O3,and then oxidize the partially dehydrogenated intermediates produced by the adsorbed allylic alcohols and Pd atoms to the desired alkenyl aldehyde.This work provides a promising path for the design and development of high-activity catalysts for aerobic oxidation reactions.

Effects of the Supports on Activity of Supported Nickel Catalysts for Hydrogenation of m-Dinitrobenzene to m-Phenylenediamine

The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR）, temperature-programmed desorption of hydrogen （H2-TPD） and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.

Catalytic methanation of syngas over Ni-based catalysts with different supports

Co-precipitation method was selected for the preparation of Ni/Al_2O_3, Ni/ZrO_2 and Ni/CeO_2 catalysts, and their performances in methanation were investigated in this study. The structure and surface properties of these catalysts were characterized by BET, XRD, H_2-TPD, TEM and H_2-TPR. The results showed that the catalytic activity at low temperature followed the order: Ni/Al_2O_3>Ni/ZrO_2>Ni/CeO_2. Ni/Al_2O_3 catalyst presented the best catalytic performance with the highest CH_4 selectivity of 94.5%. The characterization results indicated that the dispersion of the active component Ni was the main factor affecting the catalytic activity and the one with higher dispersion gave better performance.

Top-down synthesis strategies: Maximum noble-metal atom efficiency in catalytic materials

Top‐down synthesis has been used to prepare catalytic materials with nanometer sizes,but fabricating atomically dispersed metal catalysts remains a challenge because surface single metal atoms are prone to aggregation or coalescence.A top‐down strategy is used to synthesize atomically dispersed metal catalysts,based on supported Ag nanoparticles.The changes of the geometric and electronic structures of the Ag atoms during the top‐down process are studied using the in situ synchrotron X‐ray diffraction technique,ex situ X‐ray absorption spectroscopy,and transmission electron microscopy.The experimental results,coupled with the density functional theory calculations,demonstrate that the electronic perturbation of the Ag frontier orbitals,induced by the Ag‐O interactions at the perimeter of the metal‐support interface,is the driving force of the top‐down process.The top‐down synthesis has two important functions:to increase the number of catalytic active sites and to facilitate the study of complex reaction mechanisms(e.g.,formaldehyde oxidation)by developing single‐site model catalysts.

Promoting NO_(x)reduction via in situ activation of perovskite supported Pd catalysts under alternating lean-burn/fuel-rich operating atmospheres

Herein,we report the excellent De-NO_(x)performance of La0.7Sr0.3MnO3(LSM)perovskite-supported Pd catalysts(Pd-LSM)in alternating lean-burn/fuel-rich atmospheres using C3H6 as reductant and describe the in situ activation of the Pd catalysts via metal-support interaction(MSI)tuning.The NO_(x)reduction conversion of the Pd-LSM catalyst increased significantly from 56.1%to 90.1%and the production of N2O was suppressed.Our results demonstrated that this behavior was mainly attributed to the in situ transformation of Pd2+into Pd0 during the reaction.The generated Pd0 species could readily activate the C3H6 reductant and achieve an eight-fold higher turnover frequency than Pd2+for the reduction of NO_(x).Moreover,excessive MSIs inhibited the in situ generation of Pd0,and thereby,lowered the De-NO_(x)activity of the catalyst even at high Pd dispersion.In addition,the Pd-LSM catalysts exhibited much higher S tolerance than conventional Al_(2)O_(3)-supported catalysts.Our study provides a new approach for analyzing and designing highly active metal catalysts operated under dynamic alternating oxidizing/reducing atmospheric conditions.

Acetylene hydrochlorination over supported ionic liquid phase(SILP)gold-based catalyst:Stabilization of cationic Au species via chemical activation of hydrogen chloride and corresponding mechanisms

The activation of HCl by cationic Au in the presence of C2H2 is important for the construction of active Au sites and in acetylene hydrochlorination.Here,we report a strategy for activating HCl by the Au-based supported ionic liquid phase(Au–SILP)technology with the[N(CN)2^–]anion.This strategy enables HCl to accept electrons from[N(CN)2^–]anions in Au–[N(CN)2^–]complexes rather than from pure[Bmim][N(CN)2],leading to notable improvement in both the reaction path and the stability of the catalyst without changing the reaction triggered by acetylene adsorption.Furthermore,the induction period of the Au–SILP catalyst was shown to be absent in the reaction process due to the high Au(III)content in the Au(Ⅲ)/Au(Ⅰ)site and the high substrate diffusion rate in the ionic liquid layer.This work provides a facile method to improve the stability of Au-based catalysts for acetylene hydrochlorination.

Lentiviral vector-mediated down-regulation of IL-17A receptor in hepatic stellate cells results in decreased secretion of IL-6

AIM: To investigate the mechanism of interleukin (IL)-6 secretion through blocking the IL-17A/IL-17A recepto (IL-17RA) signaling pathway with a short hairpin RNA (shRNA) in hepatic stellate cells (HSCs) in vitro . METHODS: HSCs were derived from the livers of adul male Sprague-Dawley rats. IL-6 expression was evalu ated using real-time quantitative polymerase chain reaction and enzyme linked immunosorbent assay. The phosphorylation activity of p38 mitogen activated pro tein kinases (MAPK) and extracellular regulated pro tein kinases (ERK) 1/2 upon induction by IL-17A and suppression by IL-17RA shRNA were examined using Western blotting.RESULTS: IL-6 expression induced by IL-17A was significantly increased compared to control in HSCs (P < 0.01 in a dose-dependent manner). Suppression of IL17RA using lentiviral-mediated shRNA inhibited IL-6 expression induced by IL-17A compared to group with only IL-17A treatment (1.44 ± 0.17 vs 4.07 ± 0.43, P < 0.01). IL-17A induced rapid phosphorylation of p38 MAPK and ERK1/2 after 5 min exposure, and showed the strongest levels of phosphorylation of p38 MAPK and ERK1/2 at 15 min in IL-17A-treated HSCs. IL-6 mRNA expression induced by IL-17A (100 ng/mL) for 3 h exposure was inhibited by preincubation with specific inhibitors of p38 MAPK (SB-203580) and ERK1/2 (PD-98059) compared to groups without inhibitors preincubation (1.67 ± 0.24, 2.01 ± 0.10 vs 4.08 ± 0.59, P < 0.01). Moreover, lentiviral-mediated IL-17RA shRNA 1 inhibited IL-17A-induced IL-6 mRNA expression compared to random shRNA in HSCs (1.44 ± 0.17 vs 3.98 ± 0.68, P < 0.01). Lentiviral-mediated IL17RA shRNA 1 inhibited phosphorylation of p38 MAPK and ERK1/2 induced by 15 min IL-17A (100 ng/mL) exposure. CONCLUSION: Down-regulation of the IL-17RA receptor by shRNA decreased IL-6 expression induced by IL-17A via p38 MAPK and ERK1/2 phosphorylation in HSCs. Suppression of IL-17RA expression may be a strategy to reduce the inflammatory response induced by IL-17A in the liver.

结合化学知识探讨ATP水解放能实质

结合化学学科知识,从基团转移、化学键的断裂和形成等方面,阐明了ATP作为活化载体分子的实质就是在磷酰基(-PO_(3)^(2-))和磷酸基团(-OPO_(3)^(2-))转化过程中,将多余的能量用于物质结合过程;从化学键的角度,阐明了ATP提供生命活动能量的实质是在酶的催化下,通过化学键的断裂和生成过程中产生的自由能负差,促进物质合成反应的进行;从热力学角度,阐明ATP分子耦合细胞内化学反应的生理机制。