Plant Copper Amine Oxidases: Key Players in Hormone Signaling Leading to Stress-Induced Phenotypic Plasticity

Polyamines are ubiquitous, low-molecular-weight aliphatic compounds, present in living organisms and essential for cell growth and differentiation. Copper amine oxidases (CuAOs) oxidize polyamines to aminoaldehydes releasing ammonium and hydrogen peroxide, which participates in the complex network of reactive oxygen species acting as signaling molecules involved in responses to biotic and abiotic stresses. CuAOs have been identified and characterized in different plant species, but the most extensive study on a CuAO gene family has been carried out in Arabidopsis thaliana. Growing attention has been devoted in the last years to the investigation of the CuAO expression pattern during development and in response to an array of stress and stress-related hormones, events in which recent studies have highlighted CuAOs to play a key role by modulation of a multilevel phenotypic plasticity expression. In this review, the attention will be focused on the involvement of different AtCuAOs in the IAA/JA/ABA signal transduction pathways which mediate stress-induced phenotypic plasticity events.     

Mechanism in chlorine-enhanced Pd catalyst for H2O2 in situ synthesis in electro-Fenton system

Palladium-based catalysts have been widely employed in the electro-Fenton process for in situ generation of H₂O₂. However, the process is still far from being practical on a large scale. In this work, a series of Cl_xFePd/γ-Al₂O₃/Al catalysts were prepared by a three-step-impregnation method. They exhibited excellent activity in H₂O₂ in situ synthesis and high efficiency in phenol degradation. The characterization results showed that Cl could assist in increasing the content of Pd⁰ and reducing the isoelectric point of catalysts, which led to the drastic promotion in the synthesis of H₂O₂. Theoretical calculations further demonstrated that Cl doping could facilitate the main reaction in H₂O₂ synthesis, as well as inhibit side reactions such as dissociation of the O O bond. Furthermore, kinetic models were proposed and fitted. A plausible reaction mechanism as well as degradation pathways were elaborated based on electron spin resonance and gas chromatography–mass spectrometry results. These findings illustrate the value of palladium-based Cl_xFePd/γ-Al₂O₃/Al catalysts for their application in the electro-Fenton process.     

Wavelength-dependent photoactivity of ZnxCd1−xS and ZnCo2O4/ZnxCd1−xS for H2 and H2O2 production

Zinc cadmium sulfide (Zn_xCd_1?xS) is a good photocatalyst for hydrogen evolution reaction (HER), but an optimum x (x_m) at which a maximum HER rate is reached varies from one report to another. In this work, we examine the effect of light wavelength, not only for the HER to H₂ in the presence of Na₂S and Na₂SO₃, but also for oxygen reduction reaction (ORR) without addition of any sacrifices. For the HER under a 365 and 420 nm LED lamp, the x_m were 0.9 and 0.7, respectively. For the HER under a 330 and 395–515 nm cut-off xenon lamp, the x_m were 0.7 and 0.5, respectively. For the ORR under a 420 nm cut-off halogen lamp, a maximum production of H₂O₂ was observed at x = 0.3. Furthermore, after 4% ZnCo₂O₄ loading, Zn_xCd_1?xS had an increased activity and stability, either for the HER or for the ORR. Through a (photo)electrochemical measurement, it is proposed that the photocatalytic activity of Zn_xCd_1?xS is determined by its light absorptivity and electron reactivity. The improved performance of n-type Zn_xCd_1?xS by p-type ZnCo₂O₄ is due to formation of a p-n junction, promoting the HER (ORR) on Zn_xCd_1?xS, and the sulfide (water) oxidation on ZnCo₂O₄. This work highlights that Zn_xCd_1-xS is a promising photocatalyst for H₂ and H₂O₂ production, respectively.     

NiFe layered double hydroxide as an efficient bifunctional catalyst for electrosynthesis of hydrogen peroxide and oxygen

Two electron oxygen reduction reaction to produce hydrogen peroxide (H₂O₂) is a promising alternative technique to the multistep and high energy consumption anthraquinone process. Herein, Ni–Fe layered double hydroxide (NiFe-LDH) has been firstly demonstrated as an efficient bifunctional catalyst to prepare H₂O₂ by electrochemical oxygen reduction (2e^? ORR) and oxygen evolution reaction (OER). Significantly, the NiFe-LDH catalyst possesses a high faraday efficiency of 88.75% for H₂O₂ preparation in alkaline media. Moreover, the NiFe-LDH catalyst exhibits excellent OER electrocatalytic property with small overpotential of 210 mV at 10 mA cm^?2 and high stability in 1 M KOH solution. On this basis, a new reactor has been designed to electrolyze oxygen and generate hydrogen peroxide. Under the ultra-low cell voltage of 1 V, the H₂O₂ yield reaches to 47.62 mmol g_cat^?1 h^?1. In order to evaluate the application potential of the bifunctional NiFe-LDH catalyst for H₂O₂ preparation, a 1.5 V dry battery has been used as the power supply, and the output of H₂O₂ reaches to 83.90 mmol g_cat^?1 h^?1. The excellent electrocatalytic properties of 2e^? ORR and OER make NiFe-LDH a promising bifunctional electrocatalyst for future commercialization. Moreover, the well-designed 2e^? ORR-OER reactor provides a new strategy for portable production of H₂O₂.     

常压干燥合成水玻璃基SiO_2气凝胶

以水玻璃和双氧水为原料一步合成二氧化硅湿凝胶,经老化、溶剂置换及三甲基氯硅烷修饰后,并于常压干燥后获得二氧化硅气凝胶。样品经低温N_2吸附-脱附、红外光谱和扫描电镜测试表明所得二氧化硅气凝胶具有三维多孔结构,且其比表面积可达482 m~2·g~(-1)、平均孔径为24.9nm及表观密度为0.12g·cm~(-3)。     

Solution processed,vertically aligned,AZO nanocolumn array for chemiresistive sensor application with UV-enhanced sensitivity

In this work, a wide and highly sensitive chemiresistive sensor has been developed based on the AZO nanocolumn array film. This is meant for the room detection of H₂O₂ under UV illumination. A cost-effective one step multi-layers growth process was adopted for the synthesis of the AZO nanocolumn array. The experimental studies were done by scanning electron microscopy (SEM), transmission and electron microscopy (TEM).Then X-ray diffraction confirmed that the AZO column array was closely packed, connected, vertically aligned, and polycrystalline, with a high surface area. This structure ensures better electrical conduction over random and separated nanostructures. The hall-effect measurement indicates that the AZO film was n-type, with high conductivity (3.60 × 10³ Ωcm), high carrier density (11.3 × 10²⁰cm⁻³) and with acceptable mobility (0.95 cm²/Vs). The x-ray photoemission spectroscopy suggests that the AZO film consists of a large amount of adsorbed oxygen-related species at the sheath layer of the thin-film, which is vital for sensors. By the UV light activation, sensors based on the AZO nanocolumn array exhibited enhanced H₂O₂ detection properties at room temperature. At a concentration from 15 μM to 30 mM, H₂O₂ sensitivity evaluated by relative response was remarkably increased from 15% to 36%. The operation under ambient conditions and wide range sensing shows that this chemiresistive AZO sensor is adequate for biomedical and environmental applications.     

负载型Pt-Fe/SiO_2催化剂催化环己烷一步氧化制己二酸

己二酸是合成尼龙-66和尼龙-46纤维的重要原料,并进一步用于生产许多重要的化工产品。工业上的己二酸多采用以硝酸为氧化剂的两步法合成,该工艺不仅工艺复杂,而且对设备有腐蚀作用,还会释放大量的温室气体N_2O。本文以负载型Pt/SiO_2、Fe/SiO_2和Pt-Fe/SiO_2为催化剂,采用过氧化氢和氧气为氧源,研究了环己烷一步氧化制己二酸的绿色合成路线。对催化剂进行ICP、BET比表面积、XRD、TEM等表征,结果表明,Pt-Fe/SiO_2催化剂中不存在与Pt或Fe对应的衍射峰。在最佳反应条件下,用高压釜进行了催化剂性能评价,结果表明,Pt-Fe/SiO_2催化活性略优于Pt/SiO_2和Fe/SiO_2。在环己烷转化率为28%的情况下,己二酸选择性达到33%。     

花椒风味油的制取及品质研究

以花椒果皮为原料,采用大豆油热浸法制取花椒风味油。以花椒风味油的酸价、过氧化值和感官评分为考察指标,通过单因素实验和正交实验优化制取工艺条件。采用顶空固相微萃取-气相色谱-质谱联用技术对花椒风味油和大豆油中挥发性风味成分进行测定。结果表明:制取花椒风味油的最佳工艺条件为浸提温度95℃、浸提时间20 min、花椒果皮添加量15%,在此条件下制取的花椒风味油香气浓郁、麻味足、色泽好且感官评分最高,其酸价(KOH)为0. 40 mg/g,过氧化值为5. 07 mmol/kg,感官评分为9. 1。花椒风味油中维生素E总量为1 869. 86 mg/kg,远高于大豆油中的742. 07 mg/kg;甾醇含量相较于大豆油几乎不变;脂肪酸组成与大豆油的基本相同;花椒风味油中共鉴定出9类83种挥发性风味成分,大豆油中共鉴定出8类25种挥发性风味成分,花椒风味油中挥发性风味成分主要是烯烃类和醇类(相对含量86. 99%),大豆油中主要是烯烃类和醛类(相对含量87. 26%);花椒风味油中醇类18种,占总量的40. 97%,大豆油中醇类仅1种,占总量的1. 74%;花椒风味油中醛类物质含量仅为1. 91%,而大豆油中醛类物质含量为12. 69%。     

EBHP分解飞温模型建立及控制分析

对乙苯过氧化氢(EBHP)分解构建了飞温模型,绘制有冷却和无冷却体系两种工况的飞温曲线,分析了乙苯注入、紧急冷却水通入措施对飞温的抑制作用。工艺模拟试验结果表明:该EBHP飞温模型能较好预测温度随时间的变化情况,认定120℃为系统报警温度值,140℃为系统联锁值。以某63/30万t/a的苯乙烯/环氧丙烷(SMPO)装置为例,假定EBHP进料量为1000 t/h,用EBHP飞温模型核算,乙苯注入量(w)为30%的进料量时、或者紧急冷却水通入量(w)为进料量的6.5%时,系统均能快速终止飞温,且效果明显。这一研究结果为装置的安全设计和稳定运行提供了依据。