α-磷酸氢锆-六氢吡啶的超分子插层组装及其对废水中酚的吸收研究

采用直接插入法制备了六氢吡啶(HHP)对α-Zr(HPO4)2·H2O(α-ZrP)的超分子插层复合物α-ZrP-HHP。用元素分析、红外光谱(IR)、X射线粉末衍射(XRD)和TG-DSC热分析等手段表征其结构,结果表明,六氢吡啶的插入使层间距增大了0·59nm,插入的六氢吡啶客体分子在主体底物中形成双分子层。研究了α-ZrP-HHP对含酚类物质(包括苯酚、4-氯苯酚、2,4-二氯苯酚)废水的吸附,结果表明,α-ZrP-HHP对上述三种酚类物质的吸附量呈如下规律:2,4-二氯苯酚>4-氯苯酚>苯酚。     

顺式二胺基二苯并-18-冠-6插层α-磷酸锆复合材料的制备及对锶吸附性能的研究

使用直接插层法制备了顺式二胺基二苯并18-冠-6(cis-DAmDB18C6)插层α-磷酸锆(α-ZrP)材料,通过静态吸附实验,对比了顺式二胺基二苯并18-冠-6插层磷酸锆材料和α-磷酸锆对Sr~(2+)的吸附性能。实验结果表明,二胺基二苯并-18-冠-6插层磷酸锆材料对Sr~(2+)的吸附平衡时间约48h,中性溶液高温有利于吸附,低温高酸有利于解吸,最大吸附容量为125mg·g~(-1),这种插层材料对Sr~(2+)的吸附能力优于α-磷酸锆。     

α-磷酸锆插层复合材料制备及其对Cs~+吸附性能的研究

文中采用预撑插层的方法成功的将大环化合物二苯并-21-冠-7引入α-磷酸锆(α-ZrP)材料进行预插层,获得新型二苯并-21-冠-7插层α-ZrP复合材料。由于二苯并-21-冠-7插入显著提高了α-ZrP材料对Cs~+的吸附容量,其最大可达298.2 mg·g~(-1),远优于未插层的α-ZrP材料(64.1 mg·g~(-1))。本实验的开展为新型吸附材料设计与制备提供了新的思路和线索。     

层状(脯氨酸-N-甲基膦酸-磷酸氢)锆的合成及插层性能研究

以高结晶度制备了层状(脯氨酸-N-甲基膦酸-磷酸氢)锆(α-ZPMPP)晶体(层间距为1.52nm),并研究了其常温下对正丁胺的插层性能,用元素分析、IR、XRD和TG-DSC热分析对α-ZPMPP及其插层复合物进行了表征.结果表明,层状α-ZPMPP具有形成超分子主-客体化合物的插层性能,正丁胺客体分子在主体底物中形成单分子层,并插入α-ZPMPP中,使层间距增大0.45nm,插入的正丁胺可在150～250℃被脱除.     

磷酸锆及其衍生物的离子交换性能*

α-磷酸锆（α-Zr(HPO₄)₂·H₂O, α-ZrP）、γ-磷酸锆（Zr(PO₄)(H₂PO₄)·2H₂O,缩写为γ-ZrP）及其衍生物由于在离子交换、质子传导、插层化学、催化、光化学、材料化学等领域有潜在的应用前景,因而引发了大量的研究工作。本文综述了碱金属、碱土金属、过渡金属离子等与磷酸锆及其衍生物的离子交换反应机理、热力学和动力学特性,另外也讨论了发光金属配合物与磷酸锆的离子交换反应研究进展。     

晶态层状(甘氨酸-N，N-双亚甲基膦酸-磷酸氢)锆的制备和插层

晶态层状(甘氨酸-N;N-双亚甲基膦酸-磷酸氢)锆的制备和插层;（甘氨酸-N;N-双亚甲基膦酸-磷酸氢）锆; 正丁胺; 插层     

葡萄糖及转化糖在碱性溶液中的还原作用—某些氨基酚类化合物的新法制备

(一)葡萄糖或转化糖在碱性溶液中能把硝基酚类、亚硝基酚类及对磺酸苯偶氮酚类化合物还原成为相应的氨基酚类化合物。得到正面结果的有:阾硝基苯酚、对硝基苯酚、4-硝基2-甲基苯酚、2,6-二氯-4-硝基苯酚、对亚硝基苯酚、4-亚硝基-2-甲基苯酚、α-亚硝基-β-萘酚、对磺酸苯偶氮苯酚、橙Ⅱ等九种化合物。结果可称满意。(二)间硝基苯酚与2,4-二硝基苯酚在上述条件下,得不到相应的氨基酚类化合物。     

一种亲水的酚羟基修饰聚苯乙烯树脂对酚类化合物的吸附热力学

在283-323K和研究的浓度范围内,苯酚、对甲苯酚、对氯苯酚和对硝基苯酚在亲水性的酚羟基修饰聚苯乙烯树脂（AM-1）与大孔吸附树脂（Amberlite XAD-4)上平衡吸附数据符合Freundlich吸附等温方程。酚类化合物在AM-1上的吸附容量比在Amberlite XAD-4上的吸附容量增加20%以上,这主要得益于AM-1表面的酚羟基入树脂的微孔结构。在较稀的溶液中AM-1对苯酚的吸附量比AmberliteXAD-4对苯酚的吸附量增加60%,表明AM-1对苯酚有特殊的选择性。Freundlich吸附等温线、相对吸附容量以及等量吸附焓表明,四种酚在两种树脂上的吸附是物理吸附过程。对酚类化合物被两种树脂吸附的吸附焓、自由能、吸附熵也作了测试,并对吸附行为作了合理的解释。     

庚醛改性壳聚糖的制备及其对酚类化合物的吸附性能

在相转移催化剂存在下由庚醛与壳聚糖反应生成Schiff's碱,再用NaBH4 还原制备了N-烷基化壳聚糖衍生物,改性壳聚糖(CTS)产物的结构用FTIR和XRD进行了表征,研究了它对2,4-二氯酚的吸附性能. 考察了吸附时间、溶液pH值、2,4-二氯酚浓度和改性剂用量等因素对吸附的影响. 结果表明,改性CTS具有较好的抗酸碱性能;溶液的pH值对吸附的影响较大,在pH=6.0,吸附2 h时对2,4-二氯酚的吸附量最大,酚浓度对吸附的影响符合Freundlich吸附等温方程;改性壳聚糖对2,4-二氯酚的吸附性能明显优于未改性的CTS,对质量浓度为0.6 g/L的2,4-二氯酚溶液的吸附量分别为70.0和7.7 mg/g.     

中心切割GC-MS法分析煤液化油中的酚类化合物

使用碱洗提酚法提取煤液化油中的酚类化合物,然后结合Deans Switch装置和LTM色谱柱模块,采用中心切割气相色谱(GC)-质谱(MS)法对提取的酚类化合物进行定性。采用GC建立标准曲线,对煤液化油中主要酚类化合物的质量分数进行测定,并测定了煤液化油中邻甲基苯酚、2-乙基苯酚、4-丙基苯酚和5-茚酚4种酚类化合物的加标回收率。结果表明,在煤液化油中共定性出51种酚类化合物,测定了其中的35种酚类化合物的质量分数,其量占煤液化油总量的2.54(wt)%,苯酚和烷基苯酚占35种酚类化合物的88.2(wt)%。煤液化油中4种酚类化合物的加标回收率高,重复性好。     

Investigation on the toxic interaction of chrysoidine hydrochloride–CTMAB combined contamination with calf thymus DNA

The toxic interaction of the azo dye-chrysoidine hydrochloride combined with cetyltrimethyl ammonium bromide (CTMAB) in living tissue was studied in vitro. The absorption spectrum, resonance light scattering (RLS), circular dichroism (CD) and transmission electron microscopy (TEM) results showed that the toxicity of chrysoidine hydrochloride itself to calf thymus DNA (ct-DNA) is weak, while the chrysoidine hydrochloride–CTMAB combined pollution showed obvious toxic interaction with ct-DNA. The chrysoidine hydrochloride–CTMAB combined contamination can interact with ct-DNA to form an ion-associated complex through electrostatic and hydrophobic forces. The conformation of DNA was changed in the interaction process to show toxic. The experimental results showed that the combination of chrysoidine hydrochloride–CTMAB has higher toxicity to ct-DNA than either chrysoidine hydrochloride or CTMAB individually, and the combined pollution showed a strong toxic co-effect at a dose of 3.0 × 10^?4 mol L^?1 chrysoidine hydrochloride and 1.6 × 10^?5 mol L^?1 CTMAB.     

原位插层聚合法制备聚丙烯酰胺/α-磷酸锆纳米复合材料及其结构表征

聚合物／层状无机物纳米复合材料因具有常规复合材料所没有的结构、形态及较常规聚合物基复合材料更优异的性能而引起人们的广泛关注．α-磷酸锆（α-ZrP）作为一种合成的结构规整的层状无机物，其离子交换容量（600mmol／100g）是粘土的6倍，并具有长径比可控和粒子尺寸分布较窄等特点，是制备聚合物／层状无机物纳米复合材料的优良基体．以往的研究工作主要集中于金属氧化物／α-ZrP层柱材料和聚电解质膜两类复合材料，有关聚合物／α-ZrP插层复合材料的研究报道较少．聚丙烯酰胺（PAM）是一种具有广泛用途的水溶性高分子，作为聚电解质，     

形貌可控的LaPO4:Eu3+荧光粉的制备与发光性能研究

分别以硝酸镧、多聚磷酸和磷酸二氢钠为原料,在无任何添加剂和模板的条件下,采用水热法分别合成微纳米球和纳米棒两种形貌的磷酸镧.通过场发射-扫描电子显微镜(FE-SEM),X射线衍射(XRD),红外光谱(FTIR)和荧光光谱(PL)等测试手段对以上不同形貌的样品的相结构以及微观形貌进行表征.FE-SEM测试结果表明:当以多聚磷酸为磷源时,在酸性条件下可以得到平均粒径约为2μm左右的磷酸镧微球;而当以磷酸二氢钠磷源时,在酸性条件下则可以得到纳米棒;两者的分散性良好.XRD测试结果表明:两种不同形貌的样品均为单斜晶系结构.荧光光谱分析可知:Eu3+的掺杂浓度相同时,球状样品的发光强度远大于棒状样品.     

Monodisperse REPO4 (RE = Yb, Gd, Y) hollow microspheres covered with nanothorns as affinity probes for selectively capturing and labeling phosphopeptides

Rare-earth phosphate microspheres with unique structures were developed as affinity probes for the selective capture and tagging of phosphopeptides. Prickly REPO(4) (RE = Yb, Gd, Y) monodisperse microspheres, that have hollow structures, low densities, high specific surface areas, and large adsorptive capacities were prepared by an ion-exchange method. The elemental compositions and crystal structures of these affinity probes were confirmed by energy-dispersive spectroscopy (EDS), powder X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy. The morphologies of these compounds were investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen-adsorption isotherms. The potential ability of these microspheres for selectively capturing and labeling target biological molecules was evaluated by using protein-digestion analysis and a real sample as well as by comparison with the widely used TiO(2) affinity microspheres. These results show that these porous rare-earth phosphate microspheres are highly promising probes for the rapid purification and recognition of phosphopeptides.     

Catalytic activity of myoglobin immobilized on zirconium phosphonates

The adsorption and catalytic activity of myoglobin (Mb) on zirconium phosphonates (a-zirconium benzenephosphonate (alpha-ZrBP), a-zirconium carboxyethanephosphonate (alpha-ZrCEP), and a novel layered zirconium fluoride aminooctyl-N,N-bis(methylphosphonate) (ZrC8)) were investigated. The maximum adsorption was reached after 16 h of contact and was greater on hydrophobic supports such as alpha-ZrBP and ZrC8 compared to hydrophilic supports such as alpha-ZrCEP. The equilibrium adsorption isotherms fitted the Langmuir equation, suggesting the presence of a monolayer of protein molecules on the support surfaces. The catalytic activities of free Mb and of the obtained biocomposites were studied in terms of the oxidation of two aromatic substrates, o-phenylenediamine and 2-methoxyphenol (guaiacol), by hydrogen peroxide. The oxidation catalyzed by immobilized myoglobin followed the Michaelis-Menten kinetics, similar to oxidation by free Mb. The kinetic parameters, kcat and KM, were significantly affected by the adsorption process. Mb/alpha-ZrCEP was the most efficient biocatalyst obtained, probably because of the hydrophilic nature of the support. The effect of immobilization on the stability of Mb toward inactivation by hydrogen peroxide was also investigated, and an increased resistance was found. The biocomposites obtained can be stored at 4 degrees C for months without a significant loss of catalytic activity.     

纳米晶状磷酸钙盐/Al2O3-Ti生物复合材料的制备与结构表征

0引言众所周知,钛及其合金具有优良的机械力学性能,但其生物活性不足。因此,在金属基体上涂敷一层生物活性涂层,结合金属与生物活性材料的各自优势,已成为世界各国学者研究最为活跃的生物复合材料体系之一。该体系可用于临床医学,作为人体硬组织等的修复替换材料。目前,已开发出多种在金属基体上制备生物活性涂层的工艺和方法。如:等离子沉积法[1]、离子束溅射法[2]、激光熔覆法[3]、溶胶鄄凝胶法[4]、电化学沉积与水热处理合成法[5]、电泳沉积[6]、电结晶[7]等多种方法。但现有涂层材料尚存在一些问题:(1)由于替换材料的高硬度而导致其周围硬组织坏死[8];(2)由于疲劳磨损或热膨胀不匹配引起涂层脱落[9];(3)由于异质相导致生物活性降解[10]。因此,研究新的制备工艺,开发新的生物复合材料体系就显得十分重要。考虑到Al2O3具有优异的抗磨损、耐腐蚀等性能,以及较好的生物相容性,常作为临床选用的人造硬组织承载材料[11],故在本研究工作中,我们首次采用阳极氧化与水热处理复合工艺研制酸式磷酸钙/Al2O3鄄Ti生物复合材料体系。该体系不同于由日本Ishizawa等研制的HAp/TiO2鄄Ti复合体系[12]。主要体现在两...     

Synthesis of nanocrystalline calcium phosphate in microemulsion--effect of nature of surfactants

Nanosized calcium phosphate (CP) powders have been synthesized by an inverse microemulsion system using kerosene as the oil phase, a cationic surfactant Aliquat 336, a non-ionic surfactant Tween 20 and their mixture and aqueous solutions of calcium nitrate tetrahydrate and biammonium hydrogen phosphate as the water phase. It has been found that the nature of surfactants played an important role to regulate the size and morphologies of the calcium phosphate nanoparticles. The cationic surfactant Aliquat 336 has been found to regulate the nucleation and crystal growth. The synthesized powders have been comprehensively characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Our results show that the brushite (DCPD) is the major phase comprising the calcium phosphate nanoparticles. In mixed surfactants mediated system a morphological controlled highly crystalline particles have been synthesized. Further, the role of Aliquat 336 has been established and a plausible synthetic mechanism has been proposed.     

Synthesis of β-tricalcium phosphate using sol-gel self-propagating combustion method

β-tricalcium phosphate (β-TCP) is a key component of natural bone like hydroxyapatite. Pure and uniformly nanosized β-tricalcium phosphate powders were synthesized using a sol-gel self-propagating combustion method by using citric acid as a reductant and using fuel and nitrate as the oxidant. The thermal decomposition of nitrate-citrate xero-gel was studied by thermogravimetric-differential thermal analysis (TG/DTA) and the process mechanism of self-propagating combustion were discussed. The resulting powders calcined at 1023, 1173 and 1273 K were characterized by Ca/P ratio analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that the asprepared powders were pure β-tricalcium phosphate having regular porous surface very similar to coral.     

水热合成制备Al掺杂α-MnO2纳米管及其超级电容器电化学性能

通过水热法制备了未掺杂α-MnO₂和Al 掺杂α-MnO₂, 对产物的形貌、结构和电化学性能进行了研究. 扫描电镜(SEM)和高分辨透射电镜(HRTEM)观察表明制备产物呈纳米管形态. 紫外-可见光谱分析计算了产物的能带间隙: 随着Al 的掺杂, α-MnO₂的能带间隙值降低. 以未掺杂α-MnO₂与Al 掺杂α-MnO₂作为电极材料, 通过循环伏安(CV)和恒流充放电测试电极的超级电容器性能. 在50 mA·g^-1电流密度下, 未掺杂α-MnO₂与Al 掺杂α-MnO₂电极的比电容分别达到了204.8 和228.8 F·g^-1. 电化学阻抗谱(EIS)分析表明Al 的掺杂降低了α-MnO₂在电解液中的阻抗, 有利于提高其电化学比电容. 增强的比电容及在1000个循环后仍具有良好的容量保持率,使Al 掺杂α-MnO₂在超级电容器中具有较好的应用前景.     

Effect of titania structure on the properties of its supported copper oxide catalysts

A facile and rapid microwave irradiation method was explored for the synthesis of bismuth phosphate (BiPO(4)) nanostructures with various morphologies and phases in different solvents. The BiPO(4) products were characterized by powder X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflection spectroscopy (DRS). The effect of the solvents on the formation of the BiPO(4) nanostructures was discussed on the basis of experimental results. The different BiPO(4) nanostructures exhibited different optical properties, BET surface areas and photocatalytic activities on the degradation of methyl orange (MO) under UV and visible light irradiation. The experimental results suggested that the photocatalytic activity was closely relative with the crystalline phase and band gap of BiPO(4). Hexagonal BiPO(4) nanoparticles with narrow band gap showed the highest photocatalytic performance.