Lipase‐catalyzed synthesis of aliphatic poly(β‐thioether ester) with various methylene group contents: thermal properties,crystallization and degradation

A series of novel aliphatic poly(β‐thioether ester)s with various methylene group contents were prepared by direct lipase‐catalyzed polycondensation of the monomer with an acid‐labile β‐thiopropionate group. The polycondensation reaction using immobilized lipase B from Candida antarctica was carried out in diphenyl ether at 90 °C. Poly(β‐thioether ester)s with high molecular weights of 20 500–57 000 Da and narrow polydispersities in the range 1.40–1.48 were obtained. Thermogravimetric analysis, differential scanning calorimetry and wide‐angle X‐ray diffraction were used to investigate the thermal properties and crystal structures of these polyesters. All the poly(β‐thioether ester)s were semicrystalline polymers and thermally stable up to at least 200 °C. In vitro degradation studies showed that they can rapidly degrade under acidic conditions by the hydrolysis of the β‐thiopropionate groups, suggesting their potential as acid‐degradable polymeric materials. © 2019 Society of Chemical Industry     

Fabrication of 3D structures via direct ink writing of kaolin/graphene oxide composite suspensions at ambient temperature

Kaolin/graphene oxide composite has been widely utilized in aero-space and architectural engineering applications due to its excellent mechanical property. Direct ink writing (DIW) is a freeform rapid prototyping technology that could be used to accurately fabricate the resulting size with complex shapes. In this study, we reported the DIW of kaolin/graphene oxide (GO) composite suspensions (KGCS) to assemble 3D structures at ambient temperature for the first time. The effects of GO on the chemical constitution and microstructure of kaolin suspensions were investigated. Rheology was characterized to ensure printability of KGCS. The addition of GO in kaolin suspensions quickened a flocculation structure, which dramatically changed their rheology properties. The DIW of 3D structures from the optimal KGCS sample maintained their initial shape without spreading. The flexural and compressive strengths of the dried optimal KGCS samples were obviously enhanced due to the improvement and reduction of the micro-defects compared from cured kaolin matrix.     

Burkholderia thailandensis E264/pBMTL3-tdpR发酵生产抗癌药物ThailandepsinA的研究

在伯克氏菌Bth264野生株产新型抗癌药物Thailandepsin A以及调节基因tdp R正向调控Thailandepsin A生物合成的基础上,利用基因工程菌Bth264/p BMTL3-tdp R发酵生产Thailandepsin A,以提高产量。以0.5%乳糖为诱导剂,确定最佳诱导条件:发酵15 h添加乳糖,诱导时间6 h;通过单因素实验,确定葡萄糖和胰蛋白胨作为碳氮源、装液量65/250 m L以及接种量1%;同时结合优化发酵培养基进行发酵,Thailandepsin A产量达到252.14 mg·L-1,比优化前的产量提高56%;另外在发酵过程中,添加大孔树脂HP-20原位吸附产物,Thailandepsin A产量可达283.75 mg·L-1,比不加树脂提高13.8%;最后,基于RT-PCR和比较Ct值法,基因工程菌和野生菌相比,Thailandepsin A生物合成基因tdp B、tdp C1的转录水平分别提高11.4倍和6.0倍,对应的产量增加4.6倍,从而在很大程度上说明调节基因tdp R的过表达促进生物合成基因转录水平的提高以及产量的增加。     

Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)

It was well known that solvent effect plays a very important role in the catalytic reaction. There are many theoretical studies on the solvent effect in homogeneous catalysis while there are few theoretical studies on the solvent effect in the heterogeneous catalytic reaction and there has been no work to investigate the solvent effect on furfural transformation in heterogeneous catalysis. In the present work, both the density functional calculations and the microkinetic analysis were performed to study the selective hydrogenation of furfural over Pt(111) in the presence of methanol as well as toluene and compared with that in the gas condition. The present results indicated that the methanol can enhance the adsorption strength of furfural and other oxygen-containing reaction species due to its relatively strong polarity properties and this can be a main reason for solvent-induced high activity and selectivity. Another reason is that reaction paths study showed that the presence of methanol solvent makes the dehydrogenation of furfural less thermochemical due to the fact that furfural is more stabilized than that of dehydrogenation species, and methanol also has an inhibition effect on the dehydrogenation of furfural in the kinetic aspect, and further energetic span theory proves highest activity and selectivity for hydrogenation in methanol solvent of vapor, methanol and toluene. Moreover, microkinetic model simulation demonstrated that the activity and selectivity of hydrogenation in methanol is both higher than that in vapor and toluene. The much higher activity in methanol is due to the stabilized adsorbed reactants in the surface, which leads to a higher surface coverage of furfural. It might be proposed based on the present work that a solvent with relatively strong polarity may be favorable for the high selective hydrogenation of furfural.     

Raman and X-ray photoelectron spectroscopy study on the influence of La2O3 on the melt structure of SiO2–CaO–Al2O3–MgO

In order to gain more insights into the influence of rare earth elements on the melt structure of SiO₂–CaO–Al₂O₃–MgO glass ceramics, Raman and X-ray photoelectron spectroscopy techniques were used to study the influence of La₂O₃ on the Si–O/Al–O tetrahedron structure within SiO₂–CaO–Al₂O₃–MgO–quenched glass samples in this study. Results showed that some Raman peak shapes at low frequencies (200–840 cm^?1) changed significantly after the addition of La₂O₃, compared to the high frequency (840–1200 cm^?1) region that corresponds to the [SiO₄] structure, suggesting that the depolymerization of the low-frequency T–O–T (T=Si or Al) structure was more prevalent with La³⁺ addition. Besides, the depolymerization extent of the Si–O/Al–O tetrahedral network varied when the melt composition altered. Most notably, depolymerization is the most significant at a low CaO/SiO₂ ratio (0.25) and a high Al₂O₃ content (8%). Meanwhile, La³⁺ can promote the transformation of Si–O–Si and Al–O–Al bonds to the Si–O–Al ones, thereby forming a complex ionic cluster network interwoven with Si–O and Al–O tetrahedrons.     

Effect of Li2O on the crystallization behavior of CaO-Al2O3-SiO2-Li2O-Ce2O3 mold slags

The effect of Li₂O on the crystallization properties of CaO-Al₂O₃-SiO₂-Li₂O-Ce₂O₃ slags was investigated. With increasing the Li₂O content, LiAlO₂ and CaCeAlO₄ were the main crystalline phases. LiAlO₂ formed for the charge compensating of Li⁺ ions to [AlO₄^5?]-tetrahedrons, and CaCeAlO₄ formed as a result of the charge balance of Ce³⁺ ions, Ca²⁺ ions, and [AlO₆^9?]-octahedrons. Increasing the content of Li₂O to 10%, the crystallization temperature was the highest, and the incubation time was the shortest. The crystallization ability was strong due to the three factors of strengthening the interaction between ions and ion groups, decreasing the polymerization degree, and increasing the melting temperature. Further increasing the content of Li₂O, the crystallization performance was obviously suppressed, because the melting temperature and the force between the cations and the anion groups decreased.     

两种3D打印用雾化Ti-6Al-4V粉末的对比研究

本研究分别利用水冷铜坩埚真空感应熔炼气雾化(VIGA-CC)和等离子旋转电极(PREP)两种技术制备出球形Ti-6Al-4V合金粉末,作者利用SEM、同步辐射CT扫描-三维重建和氩气含量测试等分析手段对不同粒径的Ti-6Al-4V合金粉末的孔洞缺陷和氩气含量、硬度值进行了表征。实验结果表明, VIGA-CC粉末粒度分布宽,细粉收得率较多,粉末粒度分布在40~180 μm之间, PREP粉末的粒度分布较窄,主要集中在110~180 μm之间；金属粉末内部的孔隙率、气体含量和孔尺寸随着粉末粒度的增大而增大,且同一粒径范围内VIGA-CC粉末的气孔概率多于PREP粉末；随着粉末粒径减小,粉末截面组织逐渐细化,其硬度值逐渐升高,整体上VIGA-CC粉末硬度值高于PREP粉末。     

Effect of steel slag on 3D concrete printing of geopolymer with quaternary binders

A new type of 3D-printable ‘one-part’ geopolymer was synthesized with fly ash (FA), granulated blast furnace slag (GBFS), steel slag (SS) and flue gas desulfurization gypsum (FGD). The effects of SS content (0–40%) on the rheological properties, 3D-printability, mechanical anisotropy and reaction kinetics of geopolymer were investigated. The yield stress and plastic viscosity monotonically decreased with the increasing SS content. Contrarily, the geopolymer with 10% of SS presented better extrudability, buildability and mechanical strength than those with 0, 20%, 30% and 40% of SS. This was mainly attributed to the conflicting influence of SS on geopolymerization, of which the OH^? produced by hydration of SS raised the alkalinity of the reaction system and accelerated the dissolution of SiO₄^4? and AlO₄^5?, while the low reactivity prohibited the following polymerization process. Furthermore, the 3D-printed geopolymer presented more compact microstructure and less mechanical anisotropy thanks to the crosslinking of morphologically complementary products, including N(C)-A-S-H, C–S–H, AFt and CH, formed via synergistic reaction of FA-GBFS-SS-FGD system.     

Corrosion behavior of under‐, peak‐, and over‐aged 6063 alloy: A comparative study

The mechanical property of age‐hardenable Al‐alloys is governed by the state of ageing, which determines the microstructure and consequently, their corrosion behavior which is a vital aspect for a number of applications. This article presents a comparative assessment of corrosion behavior of under‐, peak‐ and over‐aged Al‐Mg‐Si alloy. Corrosion characteristics have been determined via immersion tests in 0.1 M ortho‐phosphoric acid solution and intergranular corrosion (IGC) tests. Corroded surfaces are examined by field emission scanning electron micrographs‐energy dispersive spectroscopy and 3D optical profilometer. The obtained results reveal that the corrosion rate at a specific immersion time as well as the depth of IGC increases in the order for under‐, peak‐, and over‐aged states. Irrespective of the state of ageing, corrosion loss increases linearly but the rate of corrosion decreases rapidly with increasing immersion time. The dominant mode of corrosion in under‐aged alloy is identified as localized pitting, while peak‐aged is highly susceptible to IGC in contrast extensive pitting corrosion is observed for over‐aged alloy. The observed differences in corrosion behavior are explained considering characteristics of precipitates. Formation of β (Mg₂Si) in case of over‐aged alloy and presence of inclusions like AlFeMnSi particles are found to accelerate pitting corrosion.