EDTA—纤维微柱同时富集多种痕量元素以及电感耦合等离子体…

制备了ＥＤＴＡ－纤维滤纸片，以此做为微柱填充同时富集Ｆｅ，Ｃｕ，Ｚｎ，Ｖ，Ｐｂ，Ｃｄ，Ｃｏ和Ｎｉ等离子，结合电耦合等离子体发射光谱法（ＩＣＰ－ＡＥＳ）测定，回收率为９２～１０６％。本法富集倍数为１００以上。     

尼龙1010－聚四氢呋喃多嵌段共聚物的ESCA研究

尼龙１０１０－聚四氢呋哺多嵌段共聚物（ＰＡ－ＰＴＭＧ）是一种性能良好的聚合物。本文用Ｘ射线光电子能谱（ＥＳＣＡ）和计算机分峰技术研究了不同软硬段分子量的ＰＡ－ＰＴＭＧ的表面化学组成，进行了试样ＥＳＣＡ谱峰归属的确定。结果表明，本体嵌段效果较好，但在样品表面上Ｏ／Ｎ原子比大于体相Ｏ／Ｎ原子比，即软段富集于表面，并且分相程度高的试样较分相程度低的试样其软段在表面富集得更多。     

光谱法研究N-烃基吖啶满和10,10''''-二烃基-9,9''''-联二吖啶烯的氧化反应

ＵＶ，ＩＲ，ＥＳＲ和荧光光谱法研究了Ｎ－烃基吖啶满和１０，１０’－二烃基－９，９’－联二吖啶烯与π－电子受体：ＤＤＱ、ＴＣＮＱ、ＴＣＮＥ、ＣＡ的氧化反应过程，提出了它们的氧化反应机理。     

流动注射（FI）—在线柱预富集ICP—AES体系中的去溶效应研究

本文设计了一种简易的加热／冷凝去溶装置，并使之与流动注射（ＦＩ）－柱预富集－ＩＣＲＰ－ＡＥＳ）体系联接。研究了在不同情况下进样体积、去溶温度、载液流速等对分析信号强度、检出限和精密度的影响，并与非去溶体系相比较，去溶温度为１２０℃时，体系的去溶效率为３４．２％，进样效率为７２．５％；方法的检测限比非去溶体系改善近７倍。实验结果还表明，ＦＩ－柱预富集－去溶ＩＣＰ－ＡＥＳ体系获得了ｎｇ／ｍｌ～亚ｎｇ／     

ICP—AES法直接测定高纯Eu2O3中14种稀土元素

建立了ＩＰＣ－ＡＥＳ测定高纯Ｅｕ２Ｏ３中１４种稀土元素的方法，用正交设计法优化仪器测量条件，实验了基体Ｅｕ２Ｏ３对被测元素的干扰和对方法测定下限的影响。１４个稀土元素的测定下限为：Ｙｂ２Ｏ３０．５μｇ．ｇ＾－１，Ｙ２Ｏ３１μｇ．ｇ＾－１，Ｄｙ２Ｏ３，Ｈｏ２Ｏ３，Ｔｍ２Ｏ３和Ｎｄ２Ｏ３５μｇ．ｇ＾－１、Ｇｄ２Ｏ３、Ｓｍ２Ｏ３、Ｅｒ２Ｏ３、Ｃｅ２Ｏ３、Ｐｒ６Ｏ１１和Ｌａ２Ｏ３１０μｇ．ｇ＾－１，Ｌｕ２     

2，4，6－三芳基－N－取代吡啶盐的~（13）CNMR研究

用￣（１３）Ｃ－￣１ＨＣＯＳＹ、２Ｄ－Ｊ分解谱并结合选择性质子去偶以及ＤＥＰＴ技术对２５个新的２，４，６－三芳基－Ｎ－取代吡啶四氟硼酸盐的￣（１３）ＣＮＭＲ谱进行了归属，讨论了影响化学位移的因素。     

岩石中稀土元素的分离富集及荧光X－射线光谱法测定

文中用合成的偶氮氯磷－ｍＡ螯合形成纤维（以下称ＣＰＡ－ｍＡ纤维）对地质样品中的稀土元素进行分离富集，并制成薄试样进行荧光Ｘ－射线光谱法测定［１，２］。ＣＰＡ－ｍＡ纤维合成简单，交换速度快，在抗坏血酸和混合掩蔽剂（ＥＤＴＡ＋ＣＹＤＴ＋ＥＧＴＡ）存在下使痕量稀土元素及基体分离并得以富集。分析结果表明该方法的ＲＳＤ小于１５．６８％，标准加入回收率在８４．０～１０７．５％之间，能较好地满足地质工作的需要。     

自装CCD—ICP—OES仪器软件：2.软件算法基础

本文是在前文基础上,报道了用于自装ＣＣＤ－ＩＣＰ－ＯＥＳ仪器软件的Ｓ－Ｇ平滑法、差谱法、Ｋａｌｍａｎ滤波法及人工神经元网络的算法基础。     

流动注射（FI）－在线柱预富集ICP－AES体系中的去溶效应研究

本文设计了一种简易的加热／冷凝去溶装置，并使之与流动注射（ＦＩ）－柱预富集－ＩＣＰ－ＡＥＳ体系联接。研究了在不同情况下进样体积、去溶温度、载液流速等对分析信号强度、检出限和精密度的影响，并与非去溶体系相比较。结果指出，去溶温度为１２０℃时，体系的去溶效率为３４．２％，进样效率为７２．５％；方法的检测限比非去溶体系改善近７倍。实验结果还表明，ＦＩ－柱预富集－去溶ＩＣＰ－ＡＥＳ体系获得了ｎｇ／ｍｌ～亚ｎｇ／ｍｌ级的检出限，可望用于超痕量组分的测定。     

ICP—AES测定核纯海绵锆中17个杂质元素方法的研究

应用ＩＣＰ－ＡＥＳ法，对核纯海绵锆中１７个杂质元素的测定进行了试验研究。取样量１００ｍｇ时，Ａｌ、Ｃａ、Ｃｏ、Ｃｒ、Ｃｕ、Ｆｅ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｉ、Ｐｂ、Ｓｎ、Ｔａ、Ｔｉ、Ｖ、Ｙ和Ｚｎ的测定范围是１０μｇ／ｇ－３２００μｇ／ｇ。回收率为９５．２％－１０６．５％。     

一维棒状纳米纤维素及光谱性质

采用稀酸预处理纤维素浆粕,结合高压均质的物理方法,制备出一维棒状纳米纤维素.通过傅里叶红外光谱(FTIR),X射线衍射(XRD),热重分析(TGA),原子力显微镜(AFM)和透射电镜(TEM)等方法对纳米纤维素光谱性能和形貌结构进行了表征.结果表明,制得的纳米纤维素与纤维素浆粕具有相同的红外特征官能闭,但分子内氢键缔合作用被部分破坏.纳米纤维素与纤维素浆粕同属于纤维素I的晶形类型,结品度从59%提高至70%,仍保持结晶区与无定形区共存的状态.纳米纤维素的分解温度为330℃,热稳定性低于纤维素浆粕,失重温度从292℃持续至500℃,有两个明显失重阶段.纳米纤维素长度为数百纳米,宽度为数十纳米的棒状形态,易产生团聚现象.     

Polymerization of aniline on bacterial cellulose and characterization of bacterial cellulose/polyaniline nanocomposite films

Bacterial cellulose/polyaniline nanocomposite film was prepared by the chemical oxidative polymerization of aniline with bacterial cellulose. Polyaniline conducting polymer nanocomposite films with bacterial cellulose fibers was prepared and characterized. In nanocomposite film, the bacterial cellulose was fully encapsulated with polyaniline by direct polymerization of the respective monomers using the oxidant and dopant. These bacterial cellulose/polyaniline nanocomposite films materials exhibited the inherent properties of both components. The deposition of a polyaniline on the bacterial cellulose surface was characterized by SEM. XPS revealed a higher doping level of the nanocomposite films doped with p-TSA dopant. From the cyclic voltammetry results, the polyaniline polymer was thermodynamically stable because redox peaks of electrochemical transitions in the voltagrams were maintained in bacterial cellulose/polyaniline nanocomposite films.     

竹基纤维素Ⅱ氢键结合的近红外光谱研究

纤维素是一种可再生天然亲水性高聚物,其庞大的氢键网格形成多种不同的晶体结构形式。在其五种结晶变体（纤维素Ⅰ,Ⅱ,Ⅲ,Ⅳ和Ⅹ）中,纤维素Ⅱ由纤维素Ⅰ（天然纤维素）经再生或丝光化处理获得,是表面自由能最低、性能最稳定的纤维素,这主要归因于纤维素Ⅱ具有与纤维素Ⅰ晶型平行链结构相反的反平行链结构,且相比于纤维素Ⅰ有附加的分子间氢键。基于近红外光谱（NIRS）对含氢基团的敏感性及纤维素的结晶结构中有大量氢键,使通过NIRS定性检测、定量评价纤维素的结晶结构成为可能。目前,用NIRS对纤维素结晶变体氢键结合的研究甚少,针对竹材纤维素Ⅱ及其衍生材料氢键结合的研究国内外尚未见相关报道。用竹材制备纤维素Ⅰ,经丝光化处理得到竹基纤维素Ⅱ,通过NIRS研究其氢键结合状况,结果与竹粉及竹基纤维素Ⅰ相比较。此外,研究还通过NIRS对竹粉及竹基纤维素的结晶度做了定量评价。结果表明：(1）在无定形区,竹基纤维素Ⅰ、Ⅱ和竹粉相比光谱差异不大,氢键结合只有量的变化,而无质的差异;(2）在半结晶区,与竹粉相比,竹基纤维素Ⅰ晶型结构保持不变,而竹基纤维素Ⅱ形成双峰;(3）在纤维素结晶区的近红外谱带范围内,反映竹基纤维素Ⅰ结晶表面纤维素分子内氢键O2-H2···O6的强氢键结合的羟基伸缩振动的一次倍频吸收峰由6 292 cm-1向高波数转移到6 354 cm-1,该处与竹基纤维素Ⅱ形成的强氢键结合的分子间氢键O2-H2···O2反平行构造相对应;(4）NIRS预测的结晶度与XRD分析结果有良好相关性。上述结果表明,纤维素结晶区内的氢键结合在近红外特征谱带出现转移且在半结晶区形成双峰,是区别竹基纤维素Ⅱ和Ⅰ的主要特征。研究也表明NIRS对探讨纤维素多种变体的氢键结合及结晶度预测是可靠的。     

聚倍半硅氧烷以不同方式改性纤维素绝缘纸的机理研究

本文运用分子动力学方法,建立了纯纤维素模型和一系列聚倍半硅氧烷以不同方式改性的纤维素绝缘纸模型,并对其热力学性能进行了计算、对比和讨论. 实验结果表明,各聚倍半硅氧烷纤维素改性模型的性能均优于未改性模型,并且当两条纤维素分子链作为取代基通过化学键接枝在聚倍半硅氧烷分子上(M2模型)时,改性效果最佳,其内聚能密度与溶解度参数的值相较于未改性模型提高了9%,拉伸模量、体积模量、剪切模量、柯西压的值分别提升了38.6%、29.5%、41.1%和29.5%,此外本文还计算并分析了各模型的自由体积分数和均方位移,结果显示,相较于其他模型,M2模型中的化学键在避免使纤维损失强度的同时,增加了分子链间的纠缠,使纤维素分子链占据了更多自由体积,从而使体系具有更小的自由体积分数,抑制了纤维素的链运动,进而提升了纤维素绝缘纸的热稳定性,这从微观角度解释了化学处理影响改性效果的机理.     

Hydrolysis of Microcrystalline Cellulose to Produce Fermentable Monosaccharides by Plasma Acid

Plasma acid was obtained by treating distilled water with a dielectric barrier discharge (DBD) at atmospheric pressure. The tentative relationship between discharge conditions and pH value of the plasma acid was investigated. In order to optimize the hydrolysis conditions of microcrystalline cellulose with the plasma acid, an orthogonal experiment was carried out and the colorimetric determination of 3,5-dinitro-salicylic acid was applied to measure the concentration of total reduced sugar (TRS). The results showed that the pH value of the plasma acid was related to the discharge time. The acidity of the plasma acid was maintained for several hours and then faded gradually. The microcrystalline cellulose was hydrolyzed effectively by the plasma acid and the optimal hydrolysis conditions were as follows: pH 1.42 of the plasma acid, hydrolysis temperature of 80°C and hydrolysis time of 60 min. Under these conditions, the microcrystalline cellulose with polymerization degree of 200–300 was hydrolyzed completely to produce monosaccharides, including xylose and glucose with the mole ratio of 1:35, as shown by high-performance liquid chromatography (HPLC) analysis. Moreover, the hydrolysis of luffa cellulose with polymerization degree of 500–600 was also carried out. The luffa cellulose was hydrolyzed completely to produce monosaccharides including xylose, mannose and glucose with mole ratio of 6.7:1:218. Therefore, it could be concluded that the main hydrolysis product of both types of cellulose was glucose. The glucose yield of microcrystalline cellulose was 46%, whereas for luffa cellulose it was 41%. This method was an environmentally friendly and effective method to hydrolyze cellulose.     

棒状纳米纤维素仿生矿化及光谱分析

以棒状纳米纤维素为模板,采用仿生矿化的方法制备纳米纤维素/纳米羟基磷灰石复合材料。并利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜能谱分析(SEM-EDAX)对仿生矿化前后纳米纤维素中碳、氧、钙、磷元素的变化情况及分布状态进行了表征,并探讨了纳米羟基磷灰石的生长机理。结果表明纳米纤维素表面形成了纳米羟基磷灰石;纳米纤维素的碳氧比为1.81,仿生矿化后下降为1.54;仿生矿化后纳米纤维素的钙磷比nCa/nP=1.70;纳米羟基磷灰石成核是在纳米纤维素的羟基上,并且纳米纤维素表面羟基和纳米羟基磷灰石的钙离子之间发生了配位作用。纳米羟基磷灰石较为均一的形成在纳米纤维素的基体中。通过原子力显微镜(AFM)图片可以看出,直径为20nm左右的羟基磷灰石生长在纳米纤维素的表面。     

Effects of ultrasonic conditions on the interfacial property and emulsifying property of cellulose nanoparticles from ginkgo seed shells

Cellulose microparticles from ginkgo seed shells were treated by ultrasonic treatments within the selected output powders (150–600 W) and durations (10–60 min) to produce cellulose nanoparticles. The main aim of this study was to investigate effects of ultrasonic conditions on the interfacial property and emulsifying property of those cellulose nanoparticles. Compared to ultrasonic output powers, ultrasonic durations showed the greater influence on morphology and physical properties of cellulose nanoparticles. Atomic force microscopy revealed that noodle-like cellulose particles with 1100 nm in length gradually became the short rod-like nanoparticles with 300 nm in length with increasing of ultrasonic duration from 10 min to 60 min. Moreover, results of contact angles indicated that ultrasound could significantly improve hydrophobicity of cellulose nanoparticles. The interfacial shear rheology showed that although all cellulose nanoparticles exhibited the similar interface adsorption behavior which showed the initial lag-phase of adsorption, followed by the interface saturation, the time of this initial lag-phase was affected by ultrasonic conditions. The increase of ultrasonic duration and ultrasonic power could shorten the time of this initial lag-phase, suggesting the resulting cellulose nanoparticles easier adsorption at the O/W interface. It was probably attributed to its small size and high hydrophobicity induced by intense ultrasonic treatments. Meanwhile, the cellulose nanoparticles with small size and higher hydrophobicity exhibited the better emulsifying ability to stabilize oil-in-water emulsions due to the formation of the viscoelastic interfacial film. This study improved understanding about changes in interfacial and emulsifying properties of cellulose nanoparticles caused by ultrasonic treatments.     

Controlled hydrothermal growth of ZnO nanostructures by sequestering the Zn metal ions with the chelating agent EDTA

In the present work, a controlled growth of ZnO nanostructures by manipulating Zn metal ion concentration by the chelating action of ethylene diaminetetra acetic acid in hydrothermal method is studied. EDTA produces metal–chelate complex by the formation of bidentate ligand with Zn²⁺ in the solution and diminishes the reactivity of Zn metal cations. Concentration of EDTA in the mother solution was varied in different ranges like 3, 5 and 10 mM while retaining the zinc metal salt and the NaOH concentration the same. Three different morphologies of wurtzite structured ZnO nanostructures such as nanorods-bunch, separate/discrete uniformly sized hexagonal nanorods and tapered flower petals like shapes are achieved by 3, 5 and 10 mM strengths of EDTA, respectively. The medium concentration 5 mM of EDTA is found to have moderate control over producing ZnO nanostructures of uniform diameter and a high aspect (length to diameter) ratio. An array of vertically aligned free standing ZnO nanorods with uniform spacing is successfully achieved by the addition of 5 mM of EDTA in the mother solution and the same is studied for its fluorescence property at an excitation of 325 nm and it has exhibited a characteristic UV emission of ZnO around 383 nm.     

纳米纤维素碱法制备及光谱性质

在纳米尺寸范围操控纤维素分子,由此创制出具有优异功能的新纳米材料是纤维素科学的前沿领域。纳米纤维素作为一种可再生生物材料已成为国内外研究热点,研究开发新型的简单、绿色、低能耗、快速、高效的纳米纤维素制备方法显得尤为重要。该研究采用简易可行的碱性水解法制备得到粒径较小且分散性较好的纳米纤维素。同时采用了电子显微镜、X射线粉末衍射仪和傅里叶红外光谱仪对所制备纳米纤维素进行了表征,研究了其结构与谱学性质。所制备样品为准球形纳米纤维素,颗粒尺寸约为20～40 nm,样品仍属于纤维素Ⅰ型,结晶度为79.71%,晶粒平均尺寸为3～6 nm。结果表明,碱水解法制备纳米纤维素方法具有简易可行、得率高的优点,研究可为纳米纤维素的高效制备提供一条新途径。     

Enhanced degradation of 2,4-dichlorophenol by ultrasound in a new Fenton like system (Fe/EDTA) at ambient circumstance

This study investigated the effect of ultrasound (US) enhancement on the degradation of 2,4-DCP in a new Fenton like system. An obviously synergistic effect was observed after introduction of US into the Fe/EDTA system. Good correspondences with pseudo-first-order kinetic were found in each reaction system. It was demonstrated that the degradation rate constant (k_obs) of DCP in US/Fe/EDTA was 7 and 32 times higher than those in Fe/EDTA and US system alone. Simultaneously, lower first-order k_obs was also obtained in the investigation of decomposition of EDTA. At 60 min reaction time, Removals of 81% TOC, complete DCP and 89% EDTA were achieved. Low molecular weight organic acids are identified as the main products, which contribute to the solution self-buffer at about pH 6.5 along with the reaction. In addition, the effect of initials condition, i.e., iron addition, EDTA dosage, DCP concentration and US input power as well as reaction temperature were studied and reaction activation energy (E_a) was also calculated.