二茂铁及其衍生物的合成与应用研究进展

近年来二茂铁及其衍生物的合成与应用研究是金属有机化学研究的热点.本文不仅对二茂铁及其衍生物的性质、合成及其应用研究现状作了归纳和评述,而且简要概括了二茂铁及其衍生物的未来研究方向.     

二茂铁及其衍生物作为电化学传感器的研究进展

本文对近二十年来国内外对二茂铁及其衍生物作为电化学传感器的研究进展做了较全面的综述。主要讨论了二茂铁及其衍生物修饰电极的制备、表征,介绍了二茂铁及其衍生物作为电化学传感器的应用情况,并探讨了今后的研究方向。     

二茂铁的结构和性质

一、前言随着有机过渡金属化学的发展,这方面的内容逐渐在教科书中出现。其中二茂铁是一个比较受重视的化合物。它是1951年被发现的,它及其衍生物有许多特殊性能,如能增加汽油的抗爆震性,长效助燃性,特殊的电磁性及抗辐射性等。它的发现及其特性,推动着现代有机过渡金属化学的发展。对于二茂铁的结构,一般教科书上描述比较简单,从结构的角度来解释     

1,1′-二茂铁二甲醛的合成研究

半个世纪以来,由于二茂铁及其衍生物表现出特有的芳香性、稳定性、氧化还原性及生物活性等,使得它们在材料、航天、医疗等领域得到了广泛的应用[1,2,3].     

二茂铁-Nafion修饰葡萄糖传感器的研究

1 引言 第二代电流式酶传感器采用非生理的氧化还原介体如二茂铁及其衍生物、铁氰化钾、四硫富瓦烯、醌及其衍生物、钉化合物及麦尔多蓝等代替氧,起着酶与电极之间的电子传递作用,克服了第一代电流式酶传感器背景电流大,响应特性差,易受环境中氧浓度的影响,干扰大等缺点。但目前第二代电流式酶电极还存在着介体流失,电极污染及一些电活性物质干扰等问题。商品化的Nafion甲醇溶液不易溶解酶且能使部分酶失活,本文把Nafion甲醇溶液制成Nafion水溶液,将葡萄糖氧化酶溶解在Nafion水溶液,然后把它修饰在修饰有二茂铁的玻碳电极的表面,最后再修饰一层Nafion膜,成功地制备了二茂铁-Nafion修饰葡萄糖传感器,Nafion膜不仅能把抗坏血酸、尿酸等电活性物质阻挡在电极外,防止其干扰,同时具有防污性能,而且能防止二茂铁的流失,提高电极的稳定性。该传感器具有抗干扰能力强,响应快等特点。     

微铂电极上1-酰基二茂铁动力学参数的测定

本文合成并研究了１－酰基二茂铁在ＣＨ２Ｃｌ２中的伏安行为，测定了它们在ＣＨ２Ｃｌ２中不同支持电解质浓度时的扩散系数，并分明用Ｚ．Ｇａｌｕｓ和Ｋ．Ａｏｋｉ方法计算了两种状态下的电子迁移速率常数。讨论了取代基的诱导效应和共轭效应及其链长对１－酰基二茂铁的动力学性质的影响以及支持电解质及其浓度等因素对伏安曲线的影响。     

二茂铁及其衍生物的电化学特性与结构理论研究

研究了二茂铁及其衍生物(甲酰二茂铁,乙酰二茂铁,甲醇二茂铁和乙酸二茂铁)的电化学行为,运用结构理论给出了二茂铁D5点群群轨道能级图与二茂铁衍生物的前线轨道能级图,得出在二茂铁分子结构中1e2(dx2-y2,dxy)与3a1(dz2,4s)分别属于分子前线轨道中的HOMO和LUMO。同时用密度泛函理论(DFT)在LANL2DZ基组水平上对其结构进行了全优化,得到了二茂铁及其衍生物前线最高被占轨道(HOMO)能量值,Fe原子净电荷,对其电化学行为与前线轨道能级相对大小进行了验证。     

含二茂铁基希夫碱及其配合物的研究

本文报道了含二茂铁基希夫碱-1,2-亚乙基双(二茂铁甲酰基异丙亚胺)及其某些d,f过渡金属配合物的合成,并对其结构进行了表征。     

二茂铁大环化合物研究进展

概述了氧化还原型大环化合物的特点，重点阐述了二茂铁大环化合物的研究进展及其可能的应用前景。     

漆树漆酶对共存二茂铁和亚铁氰化钾的催化氧化

漆酶是含铜金属酶,主要来源于漆树漆液(生漆)和真菌,分别称漆树漆酶和真菌漆酶。近年来,人们对漆酶的催化氧化反应的研究很感兴趣。已经发现漆酶的催化反应大多在水溶液中进行,氧化底物主要是邻、对苯二酚(胺)及其衍生物,对二茂铁(Fc-H)及其衍生物(Fc-R)的催化氧化尚不多见,对共存Fc-H和K_4Fe(CN)_6的催化氧化也未见报道,这可能与Fc-H和多数Fc-R不溶于水有关。本文选择二乙二醇单丁醚(DGBE)和磷酸盐缓冲液为混合溶剂,使Fc-H和K_4Fe(CN)_6以一定浓度共溶其中,考察了在该体系中漆树漆酶对Fc-H和K_4Fe(CN)_6的催化氧化反应。     

Development of Paper Actuators Based on Carbon-Nanotube-Composite Paper

We propose a unique soft actuator—a paper actuator—based on carbon-nanotube-composite paper (CNT-composite paper), which is a composite of carbon nanotubes (CNTs) and paper. CNT-composite paper has highly efficient properties because of the contained CNTs, such as high electrical conductivity and semiconducting properties. We are considering using CNT-composite paper for various devices. In this study, we successfully developed a paper actuator. We determined the structure of the paper actuator by referencing that of bucky-gel actuators. The actuator operates using the force generated by the movement of ions. In addition to making the paper actuator, we also attempted to improve its performance, using pressure as an index and an electronic scale to measure the pressure. We investigated the optimal dispersant for use in paper actuators, expecting the residual dispersant on the CNT-composite paper to affect the performance differently depending on the type of dispersant. Referring to research on bucky-gel actuators, we also found that the addition of carbon powder to the electrode layers is effective in improving the pressure for paper actuators. We believe that the paper actuator could be used in various situations due to its ease of processing.     

Relationship between the decrease of degree of polymerisation of cellulose and the loss of groundwood pulp paper mechanical properties during accelerated ageing

During natural ageing, paper undergoes colour changes and becomes brittle. It is mainly due to the degradation of cellulose, the main component of paper fibres. From the viewpoint of conservation/protection of paper-based information carriers, as well as of the utilisation of secondary fibres, knowledge of the impact of a decrease of the degree of polymerisation (DP) of cellulose on mechanical properties of paper becomes of key importance. In this paper, correlations between the decrease of DP of cellulose and the loss of paper folding endurance (FE) using three model samples (pure cellulose, groundwood pulp paper, and degraded groundwood pulp paper) at accelerated ageing were investigated. The existence of such correlations between DP and FE is supported by experimental results; the correlations are linear for pure cellulose and groundwood pulp paper ageing, while exponential correlation was observed in case of degraded groundwood pulp paper. The results indicate that the rate of paper degradation can be evaluated by means of the rate of glycosidic bonds breaking in cellulosic polymer chains both for cellulose and groundwood pulp paper.     

Characterization and pyrolysis behaviour of different paper mill waste materials

Paper industry generates a considerable amount of wastes. Their composition mainly depends on the type of paper produced and the origin of cellulose fibres. Nowadays, in Spain, 40% of solid wastes generated by the paper and pulp industry are deposited directly in landfill, 25% are used in the agriculture, 13% in the ceramic industry and 7% in the concrete production. In the last years, thermal treatment methods like combustion, pyrolysis and gasification have been widely study as alternative techniques for the valorization of different organic waste materials. The main objective of the present work is to study the pyrolysis behaviour of different paper mill waste materials. For this reason, a wide characterization of eight paper mill waste materials from different origins was performed using SEM, FTIR, DRX and thermogravimetric techniques. Paper mill sludges from recycled paper, mainly wastes obtained from deinking process, showed high CaCO₃ and clays contents. Compared with the elevated total organic matter content (TOM) of paper mill waste materials their low organic carbon content determined by Cr₂O₇²⁻ oxidation reveals the elevated chemical stability of organic matter, due to high content on cellulose fibres. Analysis of samples by SEM indicates that successive recycled processes of paper leads to paper mill waste materials with more degraded fibres. XRD analyses show as crystalline cellulose was present in reject and primary sludge from paper mills that produced paper from virgin wood. However, crystalline cellulose content significantly decreased in waste materials from recycled paper. Finally, thermogravimetric analysis indicates that presence or mineral matter and degradation of cellulose significantly influences their pyrolysis behaviour. In general, weight loss of paper mill waste materials started at lower temperatures than pure cellulose. In waste materials from recycled paper weight loss continues at temperatures highest than 500 °C due to kaolinite dehydration and carbonates decomposition.     

Biodeterioration of Paper: A SEM Study of Fungal Spoilage Reproduced Under Controlled Conditions

Biodeterioration phenomena represent a complex of physical and chemical alteration processes in various materials, such as those constituting the objects that represent our cultural heritage. The biodegradation of paper is conditioned by several variables such as the materials from which cellulose is obtained, the manufacturing processes employed, the occurrence of other affecting substances such as lignin or metallic compounds, and by the environmental conditions in which papers are conserved. In this study, biodeterioration of paper was artificially induced in order to evaluate the role of a range of chemical and physical variables on damage caused by cellulolytic fungi. A variable pressure SEM instrument was used to characterise paper samples with different fibre origins, and alterations obtained in vitro. Two fungal strains, Aspergillus terreus Thom and Chaetomium globosum Kunze, which are cellulolytic species frequently associated with paper spoilage, were used to produce stains with characteristics close to those observable on art objects made from paper. The stains obtained on the different samples of paper were compared at both low and high magnification, in order to visualize the macro- and microscopic characteristics of paper fibres, inorganic constituents, impurities, and the deteriorating agents related to the spoiled areas. During this survey it was observed that single paper characteristics can strongly influence the intensity and the results of the fungal action. For example, the activity of a fungal strain on paper grades containing fibres of the same origin, but with different sizing, led to the formation of profoundly different stains and alterations. Moreover fungal structures, analysed by low vacuum SEM, in areas on paper corresponding to the stains appeared in different physiological states suggesting an important effect of paper constituents on fungal growth and their sporulating ability.     

Improvement in Tensile Strength and Water Repellency of Paper after Treatment with Methyltrimethoxysilane Oligomer Using Titanium Butoxide as a Catalyst

The improvement in the tensile strength and water repellency of paper after treatment with a 2-propanol solution of a methyltrimethoxysilane (MTMS) oligomer was studied using filter paper. Titanium butoxide introduced in the solution as a catalyst effectively reacted with the MTMS oligomer, and a Si–O–Ti bond was generated inside the paper. The tensile strength of the paper was remarkably improved by this treatment of impregnation and polymerization of the MTMS oligomer. It was speculated that the reaction proceeded by consuming water that existed among the cellulose fibers by hydrogen bonding, because there was little difference in the tensile strength between the paper treated in air and the paper treated in a dry box. The methoxy groups in the MTMS oligomer demonstrated their good ability of making a three-dimensional network, and at the same time, the methyl groups in the oligomer showed their excellent water repellency. As a result, the treated paper had a good tensile strength even under wet conditions.     

水性纸品上光涂料的研究进展

水性纸品上光涂料是用于印刷品的精加工及包装材料的表面整饬的一种涂料,具有成本低、无污染、无毒无害、性能优良,运输方便等优点,是当前印刷上光涂料的主要发展方向。目前,国内的水性纸品上光涂料生产技术多样化,质量参差不齐,且成本高,耐水、耐磨、光泽度性能都达不到高档印刷品的上光要求,70%的高档水性纸品上光涂料需要依靠进口。本文系统地介绍了目前国内外水性纸品上光涂料的研究进展,总结了水性纸品上光涂料的各自特点与应用,并提出一种水性纸品上光涂料制备的新方法。     

Paper‐based Electrochemical Devices Coupled to External Graphene‐Cu Nanoparticles Modified Solid Electrode through Meniscus Configuration and their Use in Biological Analysis

This paper demonstrates, for the first time, the use of paper‐based electrochemical devices coupled to external solid working electrodes. The paper‐based electrochemical cells were fabricated using inexpensive and largely available office paper, according to a simple protocol that consists on the creation of hydrophobic barriers using paraffinized paper and preheated metal stamp. The counter and reference electrodes were integrated to the paper platform through the deposition of carbon and silver inks, respectively. The electrochemical paper analytical device (ePAD) was coupled to external glassy carbon rod electrode modified with reduced graphene oxide doped with Cu nanoparticles through meniscus configuration. The analytical usefulness of this electrochemical approach was demonstrated through the simultaneous determination of paracetamol and caffeine in biological samples. The analytes were successfully quantified in real urine samples and limits of detection of 24.6 nM (paracetamol) and 36.1 nM (caffeine) were obtained. The paper platform showed good stability (RSD of 1.07 % for the peak currents and 1.43 % for the peak potentials) and satisfactory performance. The use of solid electrodes coupled to paper electrochemical devices, firstly demonstrated here, opens new possibilities for the utilization of ePADs in electrochemistry and electroanalytical chemistry and offers advantages such as the extremely reduced consumption of reagents and the minimal generation of wastes.     

以制浆造纸产业为平台的生物炼制新模式

本文通过分析木质生物质炼制与制浆造纸工业之间的关系,提出以制浆造纸产业为平台的生物炼制模式。在蒸煮制浆前,增加对原料预抽提处理,提取半纤维素等成分用于生产乙醇燃料和（或）其他化工化学品,抽提残渣则采用传统化学法、高得率法或有机溶剂法制浆,实现植物纤维原料多组分分离综合利用。该模式给制浆造纸产业提供一条可持续发展的新思路。     

A polyaniline-containing filter paper that acts as a sensor, acid, base, and endpoint indicator and also filters acids and bases

In this paper we report a new idea for synthesizing polyaniline in an ordinary filter paper. The synthesis was carried out by a process in which aqueous acidic aniline solution and the oxidizing agent H(2)O(2) was added to the paper drop by drop and in sequence. Uniform polymerization could be obtained with the addition of reagents in either sequence. The polymer formation led to a green coloration of the paper. Formation of the emeraldine salt of polyaniline was confirmed by UV-vis and FTIR spectroscopy. Scanning electron microscopic measurements were made for surface characterization of the polymer formed in the paper. The same paper was used as a sensor for ammonia in vapor and in solution, for acid and base as well as endpoint indication, and also to filter acids and bases. We found that, using the polymer-containing paper, ammonia concentrations in a solution as low as 14 ppm could be measured.     

Characterization of cottonseed protein isolate as a paper additive

There is current interest in using agro-based biopolymers in industrial applications. Because cottonseed protein is abundantly available, it would be useful to explore its feasibility as a polymeric additive and possible substitute for petroleum-based materials. In this work, we studied cottonseed protein isolate as a paper additive and observed its effects on the paper’s dry and wet strength. The tensile strength of paper was found to vary with the amount of the protein applied. By application of an 11% protein solution to the paper, the dry and wet strength increased by 33 and 16% compared with the paper by itself, respectively. The combined use of cottonseed protein and an acid (acetic, adipic, aspartic, and citric acids) to promote adhesion resulted in even greater dry paper strength but not in greater wet paper strength. Thermogravimetric analysis, infrared spectroscopy, and scanning electron microscopic studies suggested that the protein interacted with acid and that both components interacted with paper fibers to produce increased strength.