氧化淀粉变性基团的分析方法

介绍了淀粉工业中氧化淀粉变性基团羧基和羰基的测定方法     

直纺长丝工艺中聚酯熔体端羧基值控制的工业研究

本文从工业生产的实践出发对杜邦聚酯技术直接纺工艺中端羧基控制进行了研究。通过对熔体端羧基值对无油长丝端羧基、粘度及纺丝加工影响的分析 ,阐明了聚酯端羧基控制范围 ;通过摸索三个反应釜工艺条件对端羧基值的影响 ,找出了端羧基工业控制的有效途径 ,为同类技术装置生产提供了依据     

羧基偏氯乙烯丁苯胶乳粒子的相态结构和应用性能

以过硫酸铵为引发剂，十二烷基硫酸钠为乳化剂，采用种子聚合工艺，合成了偏氯乙烯质量分数为２３％～４３％的羧基偏氯乙烯丁苯胶乳。通过电镜观察到所合成的胶乳粒子具有核－壳结构。通过测定胶闰子表面层的羧基数量，研究了羧基的分布，结果表明，羧酸种类对羧基在胶乳粒子中及在聚合体系中的分布有重要影响，该胶乳作为地毯背衬粘合剂，具有粘合力高，极限氧指数高的特点，是一种较好的阻燃性粘合剂。     

Aqueous solution of Oxone as new oxidizing agent for multi-walled carbon nanotube functionalization

In this work, multi-wall carbon nanotube (MWCNT) was successfully modified using aqueous solution of Oxone as a new oxidant. The effect of oxidation temperature on various characteristics of the treated MWCNTs was also investigated. FTIR and titration analysis proved the formation of carboxyl, carbonyl and epoxide groups at the surface of MWCNTs. The concentration of the functional groups increased as the modification temperature increased. The presence of such oxygen containing groups at the surface of MWCNTs justified the long time stability of the treated MWCNTs suspensions in water and methanol. The modified MWCNTs showed higher entanglement compared to row MWCNT due to the cross-links adjacent effect of pendant functional groups. Finally, it was concluded that Oxone oxidation process destroys the structure of the MWCNTs, but not severe enough to unzip the MWCNTs.     

溶液法合成端羧基聚丁二烯

以过氧化戊二酸为引发剂，无水乙醇或丙酮为溶剂，采用自由基型溶液法合成了端羧基聚丁二烯，并用ＩＲ对聚合物的微观结构进行了表征。结果表明当聚合反应温度为１０５￣１１５℃时，合理搭配引发剂起始用量和连续加入引发剂的递减速率，可合成满足不同应用领域的端羧基聚丁二烯产品。     

Ionic Colloidal Molding as a Biomimetic Scaffolding Strategy for Uniform Bone Tissue Regeneration

Inspired by the highly ordered nanostructure of bone, nanodopant composite biomaterials are gaining special attention for their ability to guide bone tissue regeneration through structural and biological cues. However, bone malformation in orthopedic surgery is a lingering issue, partly due to the high surface energy of traditional nanoparticles contributing to aggregation and inhomogeneity. Recently, carboxyl‐functionalized synthetic polymers have been shown to mimic the carboxyl‐rich surface motifs of non‐collagenous proteins in stabilizing hydroxyapatite and directing intrafibrillar mineralization in‐vitro. Based on this biomimetic approach, it is herein demonstrated that carboxyl functionalization of poly(lactic‐co‐glycolic acid) can achieve great material homogeneity in nanocomposites. This ionic colloidal molding method stabilizes hydroxyapatite precursors to confer even nanodopant packing, improving therapeutic outcomes in bone repair by remarkably improving mechanical properties of nanocomposites and optimizing controlled drug release, resulting in better cell in‐growth and osteogenic differentiation. Lastly, better controlled biomaterial degradation significantly improved osteointegration, translating to highly regular bone formation with minimal fibrous tissue and increased bone density in rabbit radial defect models. Ionic colloidal molding is a simple yet effective approach of achieving materials homogeneity and modulating crystal nucleation, serving as an excellent biomimetic scaffolding strategy to rebuild natural bone integrity.     

不同氧化体系处理对多壁碳纳米管的影响

采用3种氧化体系(H2SO4/H2O2,H2SO4/K2Cr2O7,H2SO4/HNO3)对多壁碳纳米管(MWC-NTs)进行处理,通过红外光谱、拉曼光谱、热失重、滴定分析、Zeta电位激光粒度分析仪、透射电镜对氧化前后的样品进行表征.结果表明,氧化处理未明显破坏MWCNTs的管状结构,并在表面引入羧基官能团,滴定分析...     

H2+CO2 Synergistic Plasma Positioning Carboxyl Defects in g-C3N4 with Engineered Electronic Structure and Active Sites for Efficient Photocatalytic H2 Evolution

Defective functional-group-endowed polymer semiconductors, which have unique photoelectric properties and rapid carrier separation properties, are an emerging type of high-performance photocatalyst for various energy and environmental applications. However, traditional oxidation etching chemical methods struggle to introduce defects or produce special functional group structures gently and controllably, which limits the implementation and application of the defective functional group modification strategy. Here, with the surface carboxyl modification of graphitic carbon nitride (g-C₃N₄) photocatalyst as an example, we show for the first time the feasibility and precise modification potential of the non-thermal plasma method. In this method, the microwave plasma technique is employed to generate highly active plasma in a combined H₂+CO₂ gas environment. The plasma treatment allows for scalable production of high-quality defective carboxyl group-endowed g-C₃N₄ nanosheets with mesopores. The rapid H₂+CO₂ plasma immersion treatment can precisely tune the electronic and band structures of g-C₃N₄ nanosheets within 10 min. This conjoint approach also promotes charge-carrier separation and accelerates the photocatalyst-catalyzed H₂ evolution rate from 1.68 mmol h⁻¹g⁻¹ (raw g-C₃N₄) to 8.53 mmol h⁻¹g⁻¹ (H₂+CO₂-pCN) under Xenon lamp irradiation. The apparent quantum yield (AQY) of the H₂+CO₂-pCN with the presence of 5 wt.% Pt cocatalyst is 4.14% at 450 nm. Combined with density functional theory calculations, we illustrate that the synergistic N vacancy generation and carboxyl species grafting modifies raw g-C₃N₄ materials by introducing ideal defective carboxyl groups into the framework of heptazine ring g-C₃N₄, leading to significantly optimized electronic structure and active sites for efficient photocatalytic H₂ evolution. The 5.08-times enhancement in the photocatalytic H₂ evolution over the as-developed catalysts reveal the potential and maneuverability of the non-thermal plasma method in positioning carboxyl defects and mesoporous morphology. This work presents new understanding about the defect engineering mechanism in g-C₃N₄ semiconductors, and thus paves the way for rational design of effective polymeric photocatalysts through advanced defective functional group engineering techniques evolving CO₂ as the industrial carrier gas.     

Effects of Genetically Engineered Stem Cells Expressing Cytosine Deaminase and Interferon-Beta or Carboxyl Esterase on the Growth of LNCaP Prostate Cancer Cells

The risk of prostate cancer has been increasing in men by degrees. To develop a new prostate cancer therapy, we used a stem cell-derived gene directed prodrug enzyme system using human neural stem cells (hNSCs) that have a tumor-tropic effect. These hNSCs were transduced with the therapeutic genes for bacterial cytosine deaminase (CD), alone or in combination with the one encoding human interferon-beta (IFN-β) or rabbit carboxyl esterase (CE) to generate HB1.F3.CD, HB1.F3.CD.IFN-β, and HB1.F3.CE cells, respectively. CD enzyme can convert the prodrug 5-fluorocytosine (5-FC) into the activated form 5-fluorouracil (5-FU). In addition, CE enzyme can convert the prodrug CPT-11 into a toxic agent, SN-38. In our study, the human stem cells were found to migrate toward LNCaP human prostate cancer cells rather than primary cells. This phenomenon may be due to interactions between chemoattractant ligands and receptors, such as VEGF/VEGFR2 and SCF/c-Kit, expressed as cancer and stem cells, respectively. The HB1.F3.CE, HB.F3.CD, or HB1.F3.CD.IFN-β cells significantly reduced the LNCaP cell viability in the presence of the prodrugs 5-FC or CPT-11. These results indicate that stem cells expressing therapeutic genes can be used to develop a new strategy for selectively treating human prostate cancer.     

Novel Redox-Dependent Esterase Activity (EC 3.1.1.2) for DJ-1: Implications for Parkinson’s Disease

Mutations the in human DJ-1 (hDJ-1) gene are associated with early-onset autosomal recessive forms of Parkinson’s disease (PD). hDJ-1/parkinsonism associated deglycase (PARK7) is a cytoprotective multi-functional protein that contains a conserved cysteine-protease domain. Given that cysteine-proteases can act on both amide and ester substrates, we surmised that hDJ-1 possessed cysteine-mediated esterase activity. To test this hypothesis, hDJ-1 was overexpressed, purified and tested for activity towards 4-nitrophenyl acetate (pNPA) as µmol of pNPA hydrolyzed/min/mg·protein (U/mg protein). hDJ-1 showed maximum reaction velocity esterase activity (V_max = 235.10 ± 12.00 U/mg protein), with a sigmoidal fit (S_0.5 = 0.55 ± 0.040 mM) and apparent positive cooperativity (Hill coefficient of 2.05 ± 0.28). A PD-associated mutant of DJ-1 (M26I) lacked activity. Unlike its protease activity which is inactivated by reactive oxygen species (ROS), esterase activity of hDJ-1 is enhanced upon exposure to low concentrations of hydrogen peroxide (<10 µM) and plateaus at elevated concentrations (>100 µM) suggesting that its activity is resistant to oxidative stress. Esterase activity of DJ-1 requires oxidation of catalytic cysteines, as chemically protecting cysteines blocked its activity whereas an oxido-mimetic mutant of DJ-1 (C106D) exhibited robust esterase activity. Molecular docking studies suggest that C106 and L126 within its catalytic site interact with esterase substrates. Overall, our data show that hDJ-1 contains intrinsic redox-sensitive esterase activity that is abolished in a PD-associated mutant form of the hDJ-1 protein.