一种新的测定诺氟沙星的化学发光分析法

基于在碱性条件下,诺氟沙星(NFLX)对鲁米诺-过氧化氢(Luminol-H2O2)化学发光体系的化学发光信号有强烈的抑制作用,建立了一种简单、快速、可连续测定诺氟沙星的流动注射化学发光分析新方法.该方法线性范围为7.0×10-8-1.0×10-6mol/L,检出限(3σ)为1×10-8mol/L,对3.0×10-7m...     

影响鲁米诺体系电致化学发光因素的研究

系统研究了鲁米诺体系的电致化学发光行为 ,发现电学参数和溶液的酸碱性很大程度地影响电化学发光的产生、光强及连续性。确定了在碱性环境中的最佳电化学发光条件 ,发现在 KOH- KCl( p H=12 .5)介质中 ,于 Pt电极上施加 +1.3V( vs.Ag/ Ag Cl)的正矩形脉冲 ,可得到鲁米诺的最佳发光信号。发光强度与鲁米诺的浓度在 1.0× 10 -7— 1.0× 10 -5mol/ L范围内呈线性关系。并讨论了 H2 O2 及硫脲对鲁米诺的电致化学发光的影响。     

流动注射化学发光法测定过氧亚硝酸根的研究

基于碱性条件下过氧亚硝酸根-亚硫酸钠-荧光素化学发光新体系中过氧亚硝酸根浓度与化学发光强度呈线性关系,建立了流动注射化学发光法测定过氧亚硝酸根浓度的新方法。在优化实验条件下,方法的线性范围为2.384×10-6—1.192×10-4mol/L,r2=0.9994,最低检测浓度为2.384×10-6mol/L,平行测定11次相对标准偏差为0.36%。并将该方法与鲁米诺体系进行了对比,结果满意。     

流动注射化学发光测定血浆中的多巴胺

在酸性介质中,高锰酸钾氧化甲醛产生化学发光信号,当该体系中存在多巴胺时,体系发光信号显著增强,基于这一现象,建立了一种简单快速测定多巴胺的流动注射化学发光新方法.并且对试验条件进行优化.在最优条件下,多巴胺在6.0×10-8-2.0×10-5mol/L范围内与发光强度呈良好的线性关系,检出限是2.0×10-8mol/L.对2.0×10-6mol/L的多巴胺标准溶液平行测定11次,平行测得值的RSD为3.4％.将本法用于血浆中多巴胺的测定,结果令人满意.     

化学发光法测定尿酸

利用尿酸对碱性luminol-H₂O₂-Co2+化学发光体系具有较强的抑制作用,建立了一种测定尿酸的新方法。方法的线性范围为1.0×10-10～7.0×10-6 mol·L-1,检测限(3σ)为1.1×10-11 mol·L-1,RSD 1.9%(n=4,ｃ_s=5.0×10-8 mol·L-1)。该法用于人体血清及尿液中尿酸的测定,结果满意。     

鲁米诺-过氧化氢-四磺基锰酞菁化学发光体系测定依诺沙星

研究发现在碱性条件下,依诺沙星对Luminol-H2O2-四磺基锰钛菁(MnTSPc)体系的化学发光有较强的抑制作用,据此建立了流动注射化学发光测定依诺沙星药物的新方法.依诺沙星浓度在2.0×10-8-5.0×10-5mol/L范围内与发光信号的降低值(△I)呈良好的线性关系;检出限(3δ)为7.9×10-9mol/L;对于1.0×10-6mol/L依诺沙星进行11次测定,相对标准偏差为1.31%.应用于片剂中依诺沙星含量的测定,结果令人满意.     

化学发光法测定巯嘌呤的含量

在流动注射系统中,利用巯嘌呤在碱性Luminol-K₃Fe(CN)₆化学发光体系中发光信号强的特点,建立了一种测定巯嘌呤的新方法。在优化条件下,方法的线性范围是1.02×10-7～1.02×10-9mol·L-1, 回归方程是Y=36.315c+140.72(Y是相对发光强度,c是巯嘌呤浓度与10-8 mol·L-1的乘积), 相关系数是0.998 2,检出限(S/N=3)是6.33×10-10mol·L-1,RSD为3.54%（c_i=2.0×10-9mol·L-1, n=12）。该法用于合成样品的测定,简便、灵敏、快速,结果令人满意。文章简要地探讨了巯嘌呤在碱性Luminol-K₃Fe(CN)₆化学发光体系中的化学发光机理：在反应过程中,产生大量的过氧自由基和羟基自由基,自由基与鲁米诺反应,形成激发态的鲁米诺分子,鲁米诺分子由激发态回到基态产生化学发光现象。     

C60/SiO2/Chitosan复合纳米粒子的合成及其光致化学发光分析应用

采用反相微乳液纳米粒子合成方法制备了具有光致化学发光活性的C60/SiO2/Chitosan复合纳米粒子.光致化学发光研究显示该复合纳米粒子与鲁米诺的混合溶液能被波长为400 nm的光信号诱导产生鲁米诺的光致化学发光信号,且该发光信号可以被复合纳米粒子表面所吸附的DNA所抑制,据此发现,建立了检测小牛胸腺DNA的光致化学发光新方法.在最佳的实验条件下,光致化学发光信号强度与DNA浓度在1.0×10-9-1.0×10-8mol/L 之间表现出了良好线性.     

分子印迹-碳纳米管修饰电极检测扑热息痛

以扑热息痛为模板,邻苯二胺为单体,采用电聚合法制备了分子印迹-多壁碳纳米管复合膜修饰电极,研究了扑热息痛在该修饰电极上的电化学行为。结果表明,该修饰电极对扑热息痛的电极反应具有明显的电催化活性。该修饰电极对扑热息痛的方波伏安检测线性范围为2.0×10-6—8.0×10-5mol/L,检出限为1.0×10-8mol/L。该修饰电极显示了良好的稳定性和重现性。     

化学发光法测定枳壳中生物碱含量

在酸性介质中,高锰酸钾可氧化辛弗林产生化学发光,对影响化学发光强度的因素进行了实验和探讨,建立了高锰酸钾化学发光体系测定辛弗林的新方法。在最佳实验条件下,辛弗林的线性范围为4.00×10-7—2.00×10-5mol/L;检出限为6.96×10-8mol/L。该体系已经成功应用于枳壳中生物碱含量的测定,回收率为92.8%。此外,本文还测定了酸性高锰酸钾-辛弗林体系的化学发光光谱和荧光光谱,初步探讨了化学发光反应机理。     

不同绝缘层上生长的并五苯薄膜及其OTFT器件性能的研究

分别以SiO₂和PMMA为绝缘层材料制备了底栅顶接触结构的OTFT器件,得到以PMMA为绝缘层的器件具有更好的性能,其场效应迁移率为0.207 cm2·Vs-1,开关电流比为4.93×103,阈值电压为-4.3 V;而以SiO₂为绝缘层的器件,其场效应迁移率仅为0.039 cm2·Vs-1,开关电流比为5.98×102,阈值电压为-5.4 V。为分析器件性能差异的原因,测得了SiO₂和PMMA薄膜表面的AFM图谱及其上沉积并五苯薄膜后的AFM和XRD图谱。通过AFM图谱发现PMMA表面较SiO₂表面粗糙度小,其表面粗糙度的均方根值为0.216 nm,而二氧化硅薄膜表面粗糙度的均方根值为1.579 nm;且发现在PMMA上生长的并五苯薄膜的成膜质量优于在SiO₂,具有较大的晶粒尺寸和较少的晶粒间界。通过XRD图谱发现在PMMA上生长的并五苯薄膜具有明显的衍射峰,进一步证明了在PMMA上生长的并五苯薄膜具有更好的结晶状况,将更有利于载流子的传输。     

聚甲基丙烯酸甲酯等温燃烧反应的动力学研究

使用锥形量热仪研究了 3mm厚、10 0× 10 0mm2 的透明聚甲基丙烯酸甲酯 (PMMA)板在不同温度下的燃烧反应 ,采用化学动力学法拟合了PMMA燃烧过程中质量损失率a与时间t的单方程速率模型 .结果显示 ,在PMMA燃烧过程中 ,质量损失速率受产物的解吸附和扩散过程控制 .PMMA在 5 84～ 80 0℃燃烧时 ,合适的反应动力学方程为 [-ln(1-a) ]1/4=Ae-E/RTt ,其中指前因子A约等于 0 .12 39s-1,平均表观活化能E约为2 2 .81kJ/mol,并与温度的变化基本无关 ,计算结果与实验数据吻合较好     

Two-sided ignition of a thin PMMA sheet in microgravity

Numerical computations and a series of experiments were conducted in microgravity to study the ignition characteristics of a thin polymethylmethacrylate (PMMA) sheet (thicknesses of 0.2 and 0.4 mm) using a CO₂ laser as an external radiant source. Two separate ignition events were observed, including ignition over the irradiated surface (frontside ignition), and ignition, after some delay, over the backside surface (backside ignition). The backside ignition was achieved in two different modes. In the first mode, after the laser was turned off, the flame shrank and stabilized closer to the fuel surface. This allowed the flame to travel from the frontside to the backside through the small, open hole generated by the laser’s vaporization of PMMA. In the second mode, backside ignition was achieved during the laser irradiation. The numerical calculation simulating this second process predicts fresh oxygen supply flows from the backside gas phase to the frontside gas phase through the open hole, which mixes with accumulated hot MMA fuel vapor which is ignited as a second flame in the frontside gas phase above the hole. Then, the flame initiated from the second ignition travels through the hole to ignite the accumulated flammable mixture in the backside gas phase near the hole, attaining backside ignition. The first backside ignition mode was observed in 21% oxygen and the second backside ignition mode in 35%. The duration of the laser irradiation appears to have important effects on the onset of backside ignition. For example, in 21% oxygen, the backside ignition was attained after a 3 s laser duration but was not observed after a 6 s laser duration (within the available test time of 10 s). Longer laser duration might prevent two-sided ignition in low oxygen concentrations.     

Influence of ligands on the photoluminescent properties of Eu in europium β-diketonate/PMMA-doped systems

Three kinds of europium β-diketonates Eu(DBM)₃, Eu(BA)₃ and Eu(TTA)₃ (DBM: Dibenzoylmethane; BA: 1-Benzoylacetone; TTA: Thenoyltrifluoroacetone) were doped in poly(methyl methacrylate) (PMMA) matrix. The doped systems were studied by using photoluminescent (PL) spectroscopy, emission decay experiments and X-ray diffractometry. Eu(III) ions in the doped Eu(DBM)₃/PMMA systems have two distinct symmetric sites and the emission band changes greatly with the compositions. Eu(III) in the Eu(BA)₃/PMMA systems gives only one symmetric site in the doped systems and the emission band changes slightly with the compositions. Although two distinct symmetric sites of Eu(III) can be distinguished in the doped systems of Eu(TTA)₃/PMMA, the two sites have similar ⁵D₀ lifetimes and the luminescent spectra almost do not change with the compositions. XRD reveals that crystallites were formed in the doped Eu(DBM)₃/PMMA systems that have different crystalline structure from that of the chelate, and Eu(BA)₃ and Eu(TTA)₃ exist in amorphous state in the doped systems. The difference between the PL properties and structures of the doped systems for the three kinds of chelates should be attributed to different interactions between the chelate molecules and between the chelate and PMMA.     

Experimental approach to the laser machining of PMMA substrates for the fabrication of microfluidic devices

This paper deals with CO₂ laser machining of a suitable amorphous polymer (PMMA) as a flexible technique for the rapid fabrication of miniaturized structures such as microfluidic devices.A model to estimate the main dimensions (depth and width) of the grooves produced by the laser on PMMA is presented, taking into account the influence of the main process parameters (incident power, scanning speed and spot diameter). This theoretical model allows to control the engraving process showing that laser could represent a valid alternative for the production of microchannels. PMMA single-use devices are found to be easier to manufacture with respect to the conventional glass or silicon products.In a second step, IR laser vaporization is adopted for the removal of a single layer of PMMA. This is achieved using multiple overlapping sequences of straight grooves with different scanning directions. The proposed technique showed that the removal depth varied proportionally with the number of layers machined, while surface roughness is influenced by the grooves spacing and the orientation of the scanning direction between successive layers.A method for thermally bonding the PMMA sheets, constituting the 3D structure of the chip, is also presented. The combination of high temperatures and low bonding pressures makes it possible to generate a bulk junction enabling good performances in terms of sealing characteristics.     

Studies on selected polymeric materials using the photoacoustic spectroscopic technique

Polymethylmethacrylate-graft-polybisphenol-A-carbonate (PMMA-G-PC) with 50% grafting is synthesized. The graft co-polymerization of methylmethacrylate (0.036 mol · lit-1) onto polybisphenol-A-carbonate (0.5 g) in the presence of a redox couple formed from potassium persulphate (40 mol · lit-1) and thio-urea (30 mmol · lit-1) in aqueous nitric acid (0.18 M, 100 ml) in air at (45±2)°C for 3.0 h. Condensation of (PMMA-G-PC) with N- [p-(carboxyl phenyl amino acetic acid)] hydrazide (PCPH) affords polybisphenol-A-carbonate-graft-polymethylmethacrylate hydrazide (PCGH). The photoacoustic (PA) spectra of (PCGH) are recorded in a wavelength range from 200 nm to 800 nm at a modulation frequency of 22 Hz, and compared with those of pure polybisphenol-A-carbonate (PC), (PMMA-G-PC) and (PCPH). In the present work, a non-destructive and non-contact analytical method, namely the photoacoustic technique, is successfully implemented for optical and thermal characterization of selected polymeric materials. The indigenous PA spectrometer used in the present study consists of a 300-W xenon arc lamp, a lock-in amplifier, a chopper, a (1/8)-m monochromator controlled by computer and a home-made PA cell.     

新型菲涅尔线聚焦聚光太阳电池组件研究

以聚甲基丙烯酸甲脂为材料,采用热压成型工艺加工成型线聚焦菲涅尔聚光透镜(8×),可用于空间、地面光伏系统太阳电池组件的聚光系统,并对在其聚光条件下,太阳电池的电流电压特性进行测试,结果表明,该菲涅尔线聚焦棱镜能有效提高太阳电池的单位输出功率.模具的机械加工精度和光学抛光精度低,是造成其部分聚光率损失的原因.     

Fluorination of polymethylmethaacrylate with tetrafluoroethane using DC glow discharge plasma

Fluorination of polymer surfaces has technological applications in various fields such as microelectronics, biomaterials, textile, packing, etc. In this study PMMA surfaces were fluorinated using DC glow discharge plasma. Tetrafluoroethane was used as the fluorinating agent. On the fluorinated PMMA surface, static water contact angle, surface energy, optical transmittance (UV-vis), XPS and AFM analyses were carried out. After the fluorination PMMA surface becomes hydrophobic with water contact angle of 107° without losing optical transparency. Surface energy of fluorine plasma-treated PMMA decreased from 35 mJ/cm² to 21.2 mJ/cm². RMS roughness of the fluorinated surface was 4.01 nm and XPS studies revealed the formation of C-CF_x and CF₃ groups on the PMMA surface.     

第二配体对Sm(DBM)3掺杂的PMMA样品发光的影响

分别使用phen（1,10-邻菲咯啉）、TOPO（三正辛基氧化磷）、TPPO（三苯基氧化磷）作为第二配体与Sm（DBM）3（DBM：二苯甲酰甲烷）相互作用,合成了相应的配合物,然后分别将其掺入MMA中,进行聚合得到了固体样品。测量了不同第二配体样品及无第二配体样品的激发和发射光谱,对谱峰做了指认。发射谱中主要发射峰均为Sm^3＋的特征发射,有机配体的发光带很弱,说明从有机配体到稀土发光中心的能量传递非常有效。监测Sm^3＋离子644nm发射峰（^4G5/2→^6H9/2）测量了样品的激发光谱。结果显示,第二配体的加入改变了有机配体的能级结构,激发边出现明显的移动,同时紫外区的激发效率发生了变化,对发光产生了显著的影响。还测量了上述样品中Sm^3＋的^4G5/2能级的发光衰减曲线,拟合出该能级的跃迁寿命,针对不同第二配体的情况进行了比较分析。实验结果表明,第二配体的共轭性和化学键匹配对发光强度影响很大,在我们的结果中,第二配体为TPPO时发光效率最高。     

Annealing effects on the surface morphologies of thin PS/PMMA blend films with different film thickness

The surface morphology evolution of three thin polystyrene (PS)/polymethyl methacrylate (PMMA) blend films (<70 nm) on SiO_x substrates upon annealing were investigated by atomic force microscopy (AFM) and some interesting phenomena were observed. All the spin-coated PS/PMMA blend films were not in thermodynamic equilibrium. For the 67.1 and the 27.2 nm PS/PMMA blend films, owing to the low mobility of the PMMA-rich phase layer at substrate surfaces and interfacial stabilization caused by long-range van der Waals forces of the substrates, the long-lived metastable surface morphologies (the foam-like and the bicontinuous morphologies) were first observed. For the two-dimensional ultrathin PS/PMMA blend film (16.3 nm), the discrete domains of the PS-rich phases upon the PMMA-rich phase layer formed and the secondary phase separation occurred after a longer annealing time.