罗丹明6G-I~-作荧光探针研究吲哚乙酸-辣根过氧化酶催化体系中活性氧的产生机理

以罗丹明6G-I-为荧光探针,探讨了辣根过氧化酶催化吲哚乙酸体系中活性氧物种的生成,发现在此体系中可产生单线态氧、超氧、羟基自由基和过氧化氢等活性氧物种.利用活性氧氧化I-成I3-后与罗丹明6G形成离子缔合物将导致其荧光猝灭的现象,可实现活性氧物种总量的测定.相应吲哚乙酸浓度在0.21～262.8μg/mL范围内催化产生的活性氧的总量与荧光猝灭强度△F呈良好的线性关系.反应动力学研究表明,辣根过氧化酶催化吲哚乙酸产生活性氧的反应是一级反应.     

Third-order Optical Nonlinearities of a Series of Compounds Derived from a Keplerate Type Molybdenum-oxide-based Polyoxometalate

Abstract By reacting the unique Keplerate type molybdenum-oxide based polyoxometalate （NH4）42·[MoI320372·（CH3COO）30（H2O）y2]·ca.300H2·ca. 10CH3COONH4（1） with tetramethylammonium bromide, a new derivative （NH4）26[TMA]16{MoI32O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca.189H2O（2, TMA=tetramethylammonium） was prepared. Compound 2 was characterized by Fourier transform infrared spectroscopy（FTIR）, UV-Vis, elemental and thermogravimetric analyses. By the well-established Z-scan technique, investigations on the nonlinear opti- cal（NLO） properties of the series of compounds derived from the Keplerate type molybdenum-oxide-based poly- oxometalate, namely, the newly prepared compound 2, the three previously reported compounds, included compound 1, （NH4hs（TBA）24{Mo132O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca. 173H2O（3, TBA=tetrabutylammonium） and （DODA）40（NH4）2[（H2O）nMo132O372（CH3COO）3o（H20）72]（4, DODA=dimethyldioctadecylammonium）, reveal that the third-order nonlinearity[x（3）] values of compounds 1, 2 and 3 in the DMF/H2O solution and compound 4 in chloro- form are almost the same, which indicates that the counter cations with different length of alkyl chains show ignora- ble impacts on the NLO susceptibility. In other words, the remarkable third-order nonlinearities[x（3）≈10 19 m2/V2] mainly come from the [MoI32O372（CH3COO）30（H2O）72]42 anions. This fact reveals that the applications of the NLO active polyoxometalates in various environments（such as hydrophilic, hydrophobic, polar, apolar, etc.） can be achieved by simply varying cations to meet the demands in the design of diverse devices. Keywords Keplerate type polyoxometalate; Nonlinear optical property; Z-Scan technique; Self-defocusing; Reverse saturable absorption     

Preparation of TEMPO-contained pyrrole copolymer by in situ electrochemical polymerization and its electrochemical performances as cathode of lithium ion batteries

Composite electrodes based on the nitroxide free radical-contained pyrrole copolymer (PPy-co-PPy-C-TEMPO) as active material were one-step synthesized by in situ electrochemical polymerization, which was then directly applied as the cathode of lithium ion batteries. The structure, morphology, electrochemical property, and charge-discharge performances of prepared copolymers were characterized by FTIR, SEM, cyclic voltammogram, electrochemical impedance spectroscopy, and galvanostatic charge-discharge testing, respectively. The results demonstrated that PPy-co-PPy-C-TEMPO-based composite cathodes have been successfully prepared by in situ electrochemical method, and the introduction of the nitroxide free radical (TEMPO) could obviously affect the morphology and electrochemical characteristics of the obtained electroactive polymers. And the charge/discharge tests showed that with the introduction of the TEMPO, PPy-co-PPy-C-TEMPO-based composite cathodes exhibited an improved specific capacity of 70.9 mAh g^?1 for PPy-co-PPy-C-TEMPO (4:1) and 62.6 mAh g^?1 for PPy-co-PPy-C-TEMPO (8:1) as measured at 20 mA g^?1 between 2.5 and 4.2 V, which were remarkably higher than that of the pure PPy cathode of 41.0 mAh g^?1 under the same experimental conditions. Also, the obtained PPy-co-PPy-C-TEMPO copolymers demonstrated an acceptable cycling stability during the charge-discharge process. These obtained cell performances for the composite cathodes were attributed to the application of the in situ electrochemical polymerization technology, which enhanced the intimate integration between conductive polymer film and electrode. Furthermore, the introduction of TEMPO-contained pyrrole (Py-C-TEMPO) improved the morphology of the composite cathode, which was in favor of the utilization of active materials and the improved electrochemical performances.     

Cadmium sulfide nanocluster-based electrochemical stripping detection of DNA hybridization

A novel, sensitive electrochemical DNA hybridization detection assay, using cadmium sulfide (CdS) nanoclusters as the oligonucleotide labeling tag, is described. The assay relies on the hybridization of the target DNA with the CdS nanocluster oligonucleotide DNA probe, followed by the dissolution of the CdS nanoclusters anchored on the hybrids and the indirect determination of the dissolved cadmium ions by sensitive anodic stripping voltammetry (ASV) at a mercury-coated glassy carbon electrode (GCE). The results showed that only a complementary sequence could form a double-stranded dsDNA-CdS with the DNA probe and give an obvious electrochemical response. A three-base mismatch sequence and non-complementary sequence had negligible response. The combination of the large number of cadmium ions released from each dsDNA hybrid with the remarkable sensitivity of the electrochemical stripping analysis for cadmium at mercury-film GCE allows detection at levels as low as 0.2 pmol L(-1) of the complementary sequence of DNA.     

Application of solid-phase extraction: High-resolution mass spectrometry analysis strategy in the characterization and quantification of amide herbicides in aquatic products

In this study, we developed a new method combining thin-layer ultrasonic extraction, efficient SPE purification, ultra-performance liquid chromatography separation, and high-resolution mass spectrometry characterization for seven amide herbicides in fishery products. In sample preparation, to rapidly increase the contact area between the fish meat and the extractant, the fish meat was smeared on a glass slide. This process resulted in quickly reaching the extraction equilibrium and relatively high extraction efficiency. In data analysis, a strategy for characterization and qualitative analysis was constructed by analyzing the fragmentation of amide herbicides using product ion scans. Isomeric pretilachlor and butachlor were separated chromatographically, while the coeluting isomers, alachlor and acetochlor, could be separated by differences in the fragmentation of their selected precursor ions. This method overcame the challenge of poor dispersion in the extractant caused by the high viscosity of fish meat, and the challenge of separation and characterization for isomers. Compared with other methods, the extraction efficiency was improved and the amide herbicides in aquatic products was characterized and quantified rapidly and accurately. Moreover, the qualitative information was much greater and provided an additional strategy for analytes identification. This rapid and accurate method will benefit workers involved in monitoring fishery.     

基于介孔纳米碳球接枝聚胍类化合物协同光热抗菌策略的研究

细菌感染是严重威胁着人们生命健康的主要问题之一. 与传统抗生素疗法相比, 新型抗菌策略光热疗法(PTT)展现出可控、微创及不易使细菌产生耐药性的优良性能. 然而单模形式下PTT疗法并不理想, 且高温下通常伴随着炎性反应等副作用, 联合抗菌策略可有效解决这一问题. 本研究制备了富含羧基的氧化介孔纳米碳球(OMCN), 通过酰胺化反应, 共价接枝聚六亚甲基双胍(PHMB), 得到OMCN-PHMB纳米平台. 实验结果表明, OMCN的光热性能具有良好的浓度与近红外光照功率依赖性. 在808 nm激光照射下, OMCN-PHMB的体内外联合光热治疗效果显著优于单一模式下的其它治疗组, 且组织学分析结果表明, 该纳米平台对小鼠的主要器官没有产生明显的毒性, 具有较高的生物相容性.     

Association of amphipathic lignin derivatives with cellobiohydrolase groups improves enzymatic saccharification of lignocellulosics

Amphipathic lignin derivatives (ALDs), prepared from hardwood acetic acid lignin and softwood soda lignin via coupling with a mono-epoxylated polyethylene glycol, have been reported to improve the enzymatic saccharification efficiency of lignocellulose while maintaining significant residual cellulase activity after saccharification. We previously demonstrated that the effect of ALDs was caused by a direct interaction between ALDs and Cel6A (or CBH II). In this study, a different ALD was prepared from softwood kraft lignin in addition to aforementioned ALDs. The interactions between all the ALDs and the enzymes other than Cel6A, such as Cel7A and Cel7B, in a cellulase cocktail were investigated using surface plasmon resonance. The kraft lignin-based ALD showed the highest residual cellulase activity among all ALDs and an improved cellulolytic enzyme efficiency similar to those of the other ALDs. All ALDs were found to directly associate with major enzymes in the cellulase cocktail, Cel6A and Cel7A (or CBH I), but not with Cel7B (or EG I). In addition, the ALDs showed a much higher affinity to amino groups than to hydroxy and carboxy groups. In contrast, polyethylene glycol (molecular mass 4000 Da), one part of the ALD and a previously reported enzymatic saccharification enhancer, did not adsorb onto any enzymes in the cellulase cocktail or the amino group. Size exclusion chromatography demonstrated that the ALDs formed self-aggregates in both water and chloroform; the formation process in the latter was especially unique. Therefore, we conclude that the high residual cellulase activity is attributed to the direct association of ALD aggregates with the CBH group.     

用光谱层析技术重建等离子束射流场

提出了一种用光谱层析技术结合数值计算原理来重建等离子束射流温度、密度、压力和速度场的诊断方法.用CCD扫描光谱系统获得谱线强度,通过相对强度法重建温度场;再借助等离子射流有关物理方程来重建其它物理参量.分析了等离子束射流温度、密度、压力和速度场的空间分布特点以及它们之间的内在联系.     

Preparation and electrochemical characterization of Ruddlesden–Popper oxide La4Ni3O10 cathode for IT-SOFCs by sol–gel method

La₄Ni₃O₁₀ oxide was synthesized as a cathode material for intermediate-temperature solid oxide fuel cells by a facile sol–gel method using a nonionic surfactant (EO)106(PO)70(EO)106 tri-block copolymer (F127) as the chelating agent. The crystal structure, electrical conductivity, and electrochemical properties of La₄Ni₃O₁₀ were investigated by X-ray diffraction, DC four-probe method, electrochemical impedance spectra, and I–V measurements. The La₄Ni₃O₁₀ cathode showed a significantly low polarization resistance (0.26 Ω cm²) and cathodic overpotential value (0.037 V at the current density of 0.1 A cm^?2) at 750 °C. The results measured suggest that the diffusion process was the rate-limiting step for the oxygen reduction reaction. The La₄Ni₃O₁₀ cathode revealed a high exchange current density value of 62.4 mA cm^?2 at 750 °C. Furthermore, an anode-supported single cell with La₄Ni₃O₁₀ cathode was fabricated and tested from 650 to 800 °C with humidified hydrogen (～3 vol% H₂O) as the fuel and the static air as the oxidant. The maximum power density of 900 mW cm^?2 was achieved at 750 °C.     

Multi-gigahertz laser generation based on monolithic ridge waveguide and embedded copper nanoparticles

Copper(Cu)nanoparticles(NPs)are synthesized under the near-surface region of the Nd∶Y₃Al₅O₁₂(Nd:YAG)crystal by direct Cu⁺ions implantation.Subsequently,the monolithic ridge waveguide with embedded Cu NPs is fabricated by C⁴⁺ions irradiation and diamond saw dicing.The nonlinear optical response of the sample is investigated by the Z-scan technique,and pronounced saturable absorption is observed at the 1030 nm femtosecond laser.Based on the obvious saturable absorption of Cu NPs embedded Nd:YAG crystal,1μm monolithic mode-locked pulsed waveguide laser is implemented by evanescent field interaction between NPs and waveguide modes,reaching the pulse duration of 24.8 ps and repetition rate of 7.8 GHz.The work combines waveguides with NPs,achieving pulsed laser devices based on monolithic waveguide chips.