磁性珠状纤维素亲和吸附剂的制备与应用

采用反相悬浮包埋技术制备了粒径小于300um、粒径分布窄和湿态孔度高(85%～90%)的高顺磁性珠状纤维素,经高碘酸钠活化后,与具有生物活性的绒毛膜促性腺激素偶联,得磁性亲和吸附剂(每克磁性珠状纤维素上固载300～400IU绒毛膜促性腺激素).     

纤维素基磁性聚偕胺肟树脂的研究——循环吸溴中吸附与还原能力的变化

研究了酸式纤维素基磁性聚偕胺肟树脂（ＡＭＡＯ）在循环吸溴过程中吸附容量和还原能力的变化，发现原树脂的吸溴初速和溴的还原率比再生树脂高一倍以上，但第一次和第二次再生树脂的吸附速度和还原效率几乎相同，暗示着树脂吸溴后基本结构已发生了彻底的变化．树脂在循环使用时吸溴容量变化不大而溴的还原量却显著降低，表明ＡＭＡＯ作为吸溴剂有较高的实用价值．     

Application of a cellulose phosphate ion exchange membrane as a binding phase in the diffusive gradients in thin films technique for measurement of trace metals

The technique of diffusive gradients in thin films (DGT) is a newly developed analytical technique capable of measuring in situ concentrations of trace metals in the environment. The technique employs a thin film diffusive hydrogel (with well-defined diffusion properties) in contact with a binding phase capable of binding metal ions of interest. In this work, we demonstrate, for the first time, the use of a commercially available solid ion exchange membrane (Whatman P81) as the binding phase in DGT analysis. The cellulose phosphate-based Whatman P81 membrane is a strong cation exchange membrane. Its performance characteristics as a new binding phase in DGT measurement of Cu²⁺ and Cd²⁺ were systematically investigated. Several advantages over the conventional ion exchange resin-embedded hydrogel binding phases used in DGT were observed including simple preparation, ease of handling, and reusability. The binding capacities of the material to various metal ions were examined both collectively and individually. The binding phase preferentially binds to transition metal ions rather than matrix ions such as potassium, sodium, calcium and magnesium, which are competitive species in natural waters. Within the optimum pH range (pH 4.0-9.0), the maximum non-competitive binding capacities of the membrane for Cu²⁺ and Cd²⁺ were 3.22 and 3.07 μmol cm⁻², respectively. The suitability of the new membrane-based binding phase for DGT applications was validated experimentally. The experimental results demonstrated excellent agreement with theoretically predicted trends. The measurement was not degraded after four consecutive reuses of the cellulose phosphate binding phase.     

Synthesis, characterization and thermal studies on cellulose acetate membranes with additive

Cellulose acetate (CA) membranes are used in ultrafiltration applications, although they show low chemical, mechanical and thermal resistance. In order to prepare membranes with improved properties, modification of cellulose acetate with polyethelene glycol (PEG 600) has been attempted. In this study, CA has been mixed with PEG 600 as an additive in a polar solvent. The effects of CA composition and additive concentration given by a mixture design of experiments on membrane compaction, pure water flux, water content and membrane hydraulic resistance have been studied and discussed. The efficiency of protein separation by the developed CA membranes have been quantified using model proteins such as pepsin, egg albumin (EA) and bovine serum albumin (BSA). The thermal stability of the developed membranes prepared with PEG 600 additive has also been investigated using thermogravimetric analysis and differential scanning calorimetry.     

温敏性纤维素/聚Ν-异丙基丙烯酰胺复合水凝胶的固体核磁共振表征及动力学研究

利用半互穿网络方法将具有温度响应的高分子聚N-异丙基丙烯酰胺( PNIPAM)与天然纤维素复合得到温敏性水凝胶。通过固体核磁共振的1 H,13 C CP/MAS(交叉极化/魔角旋转)和QCP(定量交叉极化)等实验手段对复合凝胶的结构进行了定性及定量研究,并利用固体静态变温核磁共振实验和偶极滤波-自旋扩散实验研究了复合凝胶中PNIPAM分子链段的动力学行为。     

纤维素基吸附分离材料研究进展

以纤维素为原料制备吸附分离材料可以减少对石油资源的依赖,并具有成本低、环境友好和生物相容性好等优点。利用纤维素中的羟基基团,通过交联、接枝、引入无机粒子或与聚合物复合,可以制备出微球和薄膜等不同形态的吸附分离材料,广泛应用于生物医学,废水处理、气体分离等领域。本文结合近五年来国内外纤维素及其复合材料在吸附分离领域的研究近况,从水、油、重金属、气体和有机物的应用进行了综述,总结了纤维素基吸附分离材料的研究尚存在的问题,探讨了今后的研究方向。     

多孔炭材料在纤维素催化转化中的应用

生物质作为自然界唯一可再生的有机碳资源,其利用受到了越来越多的关注。特别是随着能源和环境危机的日益加重,将生物质中非可食用部分催化转化为燃料及具有高附加值的化学品被认为是高效、环保、原子经济的绿色过程。同时,多孔炭材料具有丰富的孔道结构、优异的水热稳定性和大比表面积,是生物质催化转化反应中最常用的载体材料之一。兼之炭材料表面极性、亲疏水性的可调变性,及对酸碱溶剂的反应惰性,也使其无论在学术研究还是在工业应用中都具有特殊的优势。另外,随着纳米炭材料科学的飞速发展,合成孔径、形貌、及表面官能团可控的介孔炭和具有多级孔道结构的多孔炭材料成为可能,将其应用到纤维素催化转化过程中,对深入理解孔道结构、表面官能团对纤维素转化的作用,揭示催化反应作用机制,指导炭基催化剂的设计合成,均具有重要意义。在本综述中,我们首先对纤维素转化中多孔炭的孔道结构和表面官能团性质的独特作用进行了阐述。由于商业活性炭的孔径一般在微孔尺度,但纤维素及可溶低聚糖的分子体积较大,因而其在活性炭中的传质受到了极大的限制。通过模板法获得的介孔炭材料,可实现孔径在2–10 nm的可控合成,大大提高了反应物的扩散速率,使之能与催化活性位有效接触。但孔道过于狭长,在反应过程中堵塞的可能性增高,进而导致催化剂失活;因此,在介孔孔道的基础上,建立互通的多级孔道结构对反应物、中间物、和产物的扩散,及催化活性的保持更为有利。另一方面,炭材料表面的含氧官能团不仅具有加强1,4-糖苷键吸附的作用,还可以作为酸性活性中心催化水解反应的进行;尤其是在传统的水相纤维素催化转化过程中,亲水表面对多孔炭催化剂与反应物的接触非常有利。本文以纤维素水解及纤维素水解加氢反应为例,展开讨论了多孔炭作为固体酸及双功能催化剂载体的应用。在水解反应中,纤维素首先在热水中降解为可溶低聚糖,之后再与活性炭表面官能团反应;其中多孔炭的比表面积、酸量、及酸强度均是促进水解发生的正向因素。在水解加氢反应中,炭载贵金属催化剂作为最常用的加氢催化剂,可获得以六元醇为主的纤维素转化产物。除了加氢作用之外,贵金属小颗粒被证实可以通过氢溢流作用提供水解所需的H+,同时,正价的贵金属也可促进反应过程中的氢转移。另一方面,由于钨物种可催化逆羟醛缩合反应的发生,因此在反应体系中引入钨物种时,水解加氢的主要产物由六元醇变为乙二醇。需要特别指出的是,在纤维素催化水解加氢的过程中,多孔炭材料作为载体同样具有非常重要的作用：一方面,三维介孔的孔道结构不仅有利于反应物、产物的扩散,也有利于加氢金属催化剂的分散,进而提高金属的催化加氢能力;另一方面,当炭材料的表面化学性质改变时,也会影响产物的选择性分布,例如当炭表面显碱性时,由于异构化作用,丙二醇成为主要产物。本文最后,我们列举了一些新型多孔炭材料,包括杂原子改性的多孔炭材料和金属氧化物-炭复合多孔材料的合成方法及其在纤维素催化转化乃至生物质转化中的潜在应用。     

Removal of multi-metals from water using reusable pectin/cellulose microfibers composite beads

Pectin (Pec) and cellulose microfibers (CF) extracted from orange waste were combined to form composite beads with enhanced adsorption capacity. Such beads were extensively tested in the removal of multi-metal ions from water. A factorial design approach was conducted to establish the optimum conditions for adsorption of Cd(II), Cu(II), and Fe(II) on Pec-CF beads. Batch adsorption experiments revealed that removal efficiency of such metal ions falls in the range of 94–58% and it followed the order Fe(II) > Cu(II) > Cd(II). The maximum Cd(II), Cu(II) and Fe(II) adsorption capacities calculated from the Langmuir isotherm were 192.3, 88.5 and 98.0 mg/g, respectively. FTIR analysis suggests that the functional groups on Pec-CF beads (binding sites) favor the adsorption of such metal ions. Desorption and reuse experiments demonstrated the beads could be used for at least five consecutive adsorption/desorption cycles. Our finds suggest the Pec-CF beads can serve as an efficient adsorbent for the removal of multi-metal ions from wastewater.     

Investigation of melamine and DOPO-derived flame retardants for the bioplastic cellulose acetate

In order to identify suitable flame retardant additives for the eco-friendly polymer cellulose acetate (CA), high-melting derivatives of the known flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were combined with the thermoplastic CA and the combustion properties were tested. CA mixtures with bis-phosphonamidates (EDA-DOPO and PIP-DOPO) showed distinct flame retardation effects and a reduction of peak heat release rates (PHRR) by up to 18%. CA mixtures with MDOP, a melamine salt of DOPA (an oxidation product of DOPO), also showed considerable effects and a reduction of PHRR by up to 27%. While producing more smoke than pure CA and CA plus melamine, owing to its aromatic component, MDOP was superior to the CA mixtures with DOPO, EDA-DOPO and PIP-DOPO in this regard. The mixture of CA with melamine gave rise to a distinctly reduced formation of toxic CO and smoke when compared with pure CA. Thus, these additives can be considered for future applications of CA-based polymers with enhanced flame protection.     

天然高分子表面活性剂

综述了淀粉、纤维素和壳聚糖类表面活性剂的合成方法、性质及功能。