Effective Release of Intracellular Enzymes by Permeating the Cell Membrane with Hydrophobic Deep Eutectic Solvents

An efficient and green method is crucial for the recovery of intracellular biological products. The major drawbacks of the conventional cell disruption method are nonselectivity and enzyme denaturation. The permeability of hydrophobic deep eutectic solvents (DESs) to the cell membrane was studied, for the first time, and then hydrophobic DESs were innovatively applied to release intracellular enzymes from recombinant Escherichia coli. After optimization, a DES suspension of l -menthol/oleic acid (0.5 %, v/v) showed the highest release yield of intracellular enzyme. Compared with that released by sonication, a release yield of phospholipase D (PLD) of up to 114.58 % was achieved, and the specific activity was increased by 1.96 times. The microstructure of the cell membrane under different treatments was observed by using an electron microscope to understand the permeation of DESs to the cell membrane. The feasibility and applicability of the proposed release method in industrial applications were also demonstrated. The effective and green release method of intracellular enzymes developed herein has bright prospects for industrial application to replace traditional cell disruption methods. A preliminary study on the permeability of hydrophobic DESs to the cell membrane showed that there would be a potential application prospect of hydrophobic DESs not only in releasing intracellular contents, but also in seeking new green penetrating agents.     

在深共熔溶剂中合成喹啉衍生物

首次在深共熔溶剂（氯化胆碱/草酸）中,通过2-氨基芳基酮与α-亚甲基酮之间的Friedländer缩合反应,合成了一系列喹啉衍生物;在80 ℃和无催化剂条件下油浴加热反应1 h,取得了62-94%的产率,深共熔溶剂重复利用3次性能无明显降低。     

Competitive growth of Al2O3/YAG/ZrO2 eutectic ceramics during directional solidification: Effect of interfacial energy

The microstructure evolution and growth behavior of the Al₂O₃/Y₃Al₅O₁₂(YAG)/ZrO₂ ternary eutectic ceramics during directional solidification were well investigated. During directional solidification of the Al₂O₃/YAG/ZrO₂ ternary eutectic ceramics, {} Al₂O₃ paralleled with {001}ZrO₂ while they did not parallel with {001}YAG at the same time in the competitive growth stage. All of the interfaces parallel to each other finally. The area percentage of the Al₂O₃/ZrO₂ and YAG/ZrO₂ interfaces are 40.4 ± 0.2% and 30.8 ± 0.1%, respectively, higher than that of the Al₂O₃/YAG (28.8 ± 0.2%). The content of Al₂O₃ and YAG phases are 39.9% and 41.1%, respectively, almost double of that of ZrO₂. The interfaces of Al₂O₃/ZrO₂ and YAG/ZrO₂ are shorter and more dispersed than that of the Al₂O₃/YAG. It was found that the interfacial energy of Al₂O₃/ZrO₂ and YAG/ZrO₂ interfaces are lower than that of Al₂O₃/YAG. It can be concluded that interfacial energy plays a decisive role in affecting the crystallographic orientation and interfaces distribution in the Al₂O₃/YAG/ZrO₂ eutectic since the interfaces of Al₂O₃/ZrO₂ and YAG/ZrO₂ with lower interfacial energy can be formed more easily during directional solidification. Therefore, the contents of Al₂O₃/ZrO₂ and YAG/ZrO₂ interfaces are higher. This study can provide theoretical guidance for interface design of multi-phase materials.     

低共熔溶剂中温度对钒离子氧化还原特性的影响

相比于传统水系电解质,低共熔溶剂（DES）因其所具有的独特优势,越来越多地被作为液流电池的电解液进行研究。DES的物理属性和电化学特性对温度较为敏感,但迄今为止对其研究较少。报道了温度对VCl₃在DES中的物理化学特性的影响。在100 mV·s^-1的扫速时,循环伏安（CV）曲线说明在25℃时,钒离子呈现准可逆的状态;随着温度从室温升高至55℃,氧化峰与还原峰之差从0.271 V降低至0.249 V。随着温度的增加,电导率也明显增加,从室温时的2.2 mS·cm^-1升高至55℃时的11.16 mS·cm^-1,而且黏度出现较大的下降。结果表明温度对DES特性的影响巨大,有必要更加深入研究温度对非水系电解液液流电池性能的影响。     

深共熔溶剂-水混合物同步提取红景天苷和酪醇的响应面优化及其分离回收

以深共熔溶剂-水混合物（LAEG40）作为提取溶剂，红景天苷提取率为主要指标，酪醇提取率为辅助指标，在前期单因素实验的基础上，利用响应面法考察了液料比、提取温度、提取时间三个主要因素对红景天中红景天苷和酪醇同步提取的影响。得到的最佳提取条件为: 液料比12.05:1(mL/g)，提取温度60 ℃，提取时间35 min。在此条件下LAEG40对红景天苷的提取率可达到19.3552?0.6604 mg/g，酪醇提取率可达到1.7211?0.0585 mg/g，远高于传统溶剂水、乙醇对红景天苷和酪醇的提取率。为实现LAEG40提取红景天苷和酪醇的回收，进行了大孔树脂吸附分离的研究。经过一系列优化，获得的最佳吸附分离条件为：选用SP-825树脂装柱，每10g树脂上样30 mL LAEG40提取液，洗脱剂选用80 %乙醇，洗脱体积40 mL，洗脱流速1 mL/min，在此条件下红景天苷和酪醇的回收率分别可达60.47 %和85.07 %。     

Thermodynamic and molecular insights into the absorption of H2S,CO2, and CH4 in choline chloride plus urea mixtures

Deep eutectic solvents (DESs) are a class of promising media for gas separation. In order to examine the potential application of DESs for natural gas upgrading, the solubilities of H₂S, CO₂, and CH₄ in choline chloride (ChCl) plus urea mixtures were measured in this work. The solubility data were correlated with Henry's law equation to calculate the thermodynamic properties of gas absorption processes, such as Henry's constants and enthalpy changes. Grand-canonical Monte Carlo simulations and quantum chemistry calculations were also performed to examine the mechanism of gas absorption processes. It is found that the absorption of H₂S in ChCl + urea mixtures is governed by the hydrogen-bond interaction between Cl of ChCl and H of H₂S, whereas the absorption of CO₂ and CH₄ in ChCl+urea mixtures is governed by the free volume of solvents. Based on the different behavior of gas absorption, high H₂S/CO₂, H₂S/CH₄, and CO₂/CH₄ selectivities can be achieved by adjusting the ratio of ChCl/urea in mixtures.     

Facile Synthesis of 7-Aryl-benzo[h]tetrazolo[5,1-b]quinazoline-5,6-dione Fused Polycyclic Compounds by Using a Novel Magnetic Polyurethane Catalyst

Novel Brönsted acid functionalized magnetic polymeric nanocomposite, Ba_0.5Sr_0.5Fe₁₂O₁₉@PU-SO₃H, has been successfully synthesized and characterized by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), Fourier transform infrared spectroscopy (FT-IR), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) techniques. The catalytic activity of the nanocomposite was tested in the regioselective synthesis of 7-aryl-benzo[h]tetrazolo [5,1-b] quinazoline-5,6-diones in an eco-friendly and recyclable media, deep eutectic solvent (DES), based on choline chloride and urea. This novel method offers several advantages, such as high yields, short reaction time, environmentally friendly reaction media, easy isolation of the product, and also offers an easy method for the synthesis of nanocatalysts. The catalyst was readily recycled by the use of an external magnetic field and could be reused 6 times without significant loss of activity or mass. DES as one of the most promising environmentally benign and cost-effective alternatives to conventional ionic liquids and volatile organic solvents was recovered from the aqueous filtrate by evaporating the water under vacuum. The recycled DES was used up to 4 runs without any loss in activity.     

Sr对Mg-1.7Si合金中初生和共晶Mg_2Si相的变质作用

为了获得性能优良的耐热镁合金,研究了Sr对初生和共晶Mg_2Si相的变质作用,并利用扫描电子显微镜观察了Mg_2Si相的形貌特征与Mg-1.7Si-x Sr合金的微观组织.结果表明,当Sr的质量分数处于1.0%~1.5%范围内时,可对初生和共晶Mg_2Si相进行有效变质.Sr的吸附作用可以诱发孪晶沟槽、旋转晶界等原子扩展台阶的出现,引起原子堆砌方式和晶体生长方向的改变,因而Sr可对初生Mg_2Si相起到变质作用.Sr的添加还可将Mg+Mg_2Si共晶的长大方式由合作长大模式变为以重新形核为主兼有合作长大的混合模式,使得Mg_2Si相的生长形态产生改变,因而Sr可对共晶Mg_2Si起到变质作用.     

Preparation and characterization of poly（lithium acrylate-arcylonitrile）／ LiClO4-LiNO3-LiBr solid polymer electrolytes

Through orthogonal experiment, a new type of LiClO₄-LiNO₃-LiBr eutectic salt with optimum mole ratio of n(LiClO₄):n(LiNO₃):n(LiBr) = 1.6:3.8:1.0 was prepared. The poly(lithium acrylate-acrylonitrile)/LiClO₄-LiNO₃-LiBr solid polymer electrolytes were prepared with poly (lithium acrylate-acrylonitrile) and LiClO₄-LiNO₃-LiBr eutectic salts. The effect of LiClO₄-LiNO₃-LiBr eutectic salts content on the conductivity of solid polymer electrolytes was studied by alternating current impedance method, and the structures of eutectic salts and solid polymer electrolytes were characterized by differential thermal analysis, infrared spectroscopy and X-ray diffractometry. The results show that the room temperature conductivity of LiClO₄-LiNO₃-LiBr eutectic salts reaches 3.11×10⁻⁴ S · cm⁻¹. The poly (lithium acrylate-acrylonitrile)/LiClO₄-LiNO₃-LiBr solid polymer electrolytes possess the highest room temperature conductivity at 70% LiClO₄-LiNO₃-LiBr eutectic salts content, and exhibit lower glass transition temperature of 75 °C compared with that of poly(lithium acrylate-acrylonitrile) of 105 °C. A complex may be formed in the solid polymer electrolytes from the differential thermal analysis and infrared spectroscopy analysis. X-ray diffraction results show that the poly(lithium acrylate-acrylonitrile) can suppress the crystallization of eutectic salts in this system.     

三元低共熔溶剂中纳米硫化铜的合成及其光催化研究

以铜粉和硫粉为原料,在摩尔比为0.48:0.32:0.2的乙酰胺,尿素,硝酸铵三元低共熔溶剂中通过单质直接反应合成了纳米CuS。通过XRD、SEM、EDS和UV-Vis DRS等手段进行了表征,XRD、EDS表明产品为纯净的CuS晶体。SEM显示产品是由纳米片交错连结而成的球体结构。UV-Vis DRS表明产品的禁带宽度为1.86 e V。测试产品的光催化降解染料性能,光照100 min后亚甲基蓝(10 mg/L)的降解率可达到100%。表明CuS具有良好的光催化活性。