纤维素基缓蚀剂的缓释机理与应用进展

简要介绍了纤维素及其衍生物的分类及其特性,综述归纳了纤维素的缓蚀机理,系统概述了植物纤维素及其衍生物,纳米纤维素在缓蚀系统中的多种缓蚀作用,同时以植物纤维素和纳米纤维素的结构特性为依据,讨论了细菌纤维素在金属缓蚀系统中的应用前景。最后提出羧甲基纤维素与羟乙基纤维素及它们各自的衍生物应用范围广,但受温度影响较大。纤维素纳米晶体在金属防护方面有很好的应用前景,也是未来研究的重点。细菌纤维素有望成为一种高效、绿色的新型缓蚀剂,但目前还未引起研究人员足够的重视,对其制备方法和缓释机理还需要进行深入研究。     

纤维素不同途径水解酸化效果对比研究

农作物秸秆结构复杂,酸化效果可能与传统糖类物料不一致。为方便考察纤维素类物料厌氧酸化效果,文章选取成分相对单一的滤纸为原料,考察了酶活浓度、反应时间、酵母菌接种量(F/M)等因素对纤维素经纤维素酶和酵母菌联合作用后的乙醇、乙酸产量的影响,及对厌氧发酵过程的影响分析。结果表明,当纤维素酶单独作用时,酶活浓度120 U/g、温度50℃、pH值4.8、水解24 h时可获得最大葡萄糖产率:73.7 mg/g(转化率为24.9%);纤维素酶和酵母菌分步糖化发酵(separate hydrolysis and fermentation,SHF)工艺中,F/M值为2:1、反应96 h可得最大乙醇产率:119.3 mg/g(转化率为42%);纤维素酶和酵母菌同步糖化发酵(simultaneous saccharification andfermentation,SSF)工艺中,F/M值为1:2、反应120 h得到最大乙醇产率:396.0 mg/g(转化率为58.2%)。F/M值为2:1、反应120 h时,SSF工艺比SHF工艺的乙醇产量提高了34.91%。     

Predicting bioavailability of PAHs in field-contaminated soils by passive sampling with triolein embedded cellulose acetate membranes

Triolein embedded cellulose acetate membrane (TECAM) was used for passive sampling of the fraction of naphthalene, phenanthrene, pyrene and benzo[a]pyrene in 18 field-contaminated soils. The sampling process of PAHs by TECAM fitted well with a first-order kinetics model and PAHs reached 95% of equilibrium in TECAM within 20 h. Concentrations of PAHs in TECAM (C_TECAM) correlated well with the concentrations in soils (r² = 0.693-0.962, p < 0.001). Furthermore, concentrations of PAHs determined in the soil solution were very close to the values estimated by C_TECAM and the partition coefficient between TECAM and water (K_TECAM-w). After lipid normalization nearly 1:1 relationships were observed between PAH concentrations in TECAMs and earthworms exposed to the soils (r² = 0.591-0.824, n = 18, p < 0.01). These results suggest that TECAM can be a useful tool to predict bioavailability of PAHs in field-contaminated soils.     

以废纸为原料制备煤尘抑制剂的合成及应用

采用碱化、醚化法制备了以废纸为原料的煤尘抑制剂,借助FTIR、SEM、TG-DTA及XRF等手段对合成物进行了表征,并将其用于抑制煤尘进行性能测试。结果表明,羧甲基纤维素的取代度为0.69;选用羧甲基纤维素含量为0.5g/mL的煤尘抑制剂进行应用实验,效果最佳。9 h内,喷洒含有羧甲基纤维素的煤尘抑制剂的煤样表面已经结壳,抗七级风,抑尘率在130 h都可保持在99%以上。在较高温燃烧条件下,煤尘抑制剂以H2O和CO2的形式失去,不会产生有害物质。     

稻秆负荷与pH对稻秆厌氧发酵产酸系统启动过程的影响

为探讨稻秆负荷（即稻秆VS/污泥VSS）与发酵pH对稻秆厌氧发酵产酸系统启动过程产挥发性脂肪酸（VFAs）效果的影响,利用厌氧搅拌罐反应系统考察在不同的稻秆负荷（0.556、0.945、1.334和1.724 g/g）和不同的发酵pH（8.0、9.0和10.0）启动运行条件下的产酸性能,并分析了系统启动过程产酸与稻秆主要成分降解之间的关系。实验结果表明,VFAs浓度随稻秆负荷提高而增大,随发酵pH的升高而降低;发酵18 d时,发酵pH为9.0时,稻秆负荷1.334 g/g的产酸效果最好,VFAs浓度与稻秆产酸量分别为4 385.10 mg/L和2.19 gVFAs/g稻秆,此时半纤维素、纤维素和酸性洗涤木质素降解率分别为32.69%、22.53%和6.40%;稻秆负荷为0.945 g/g条件下,VFAs浓度在pH为8.0时达到最高值4 409.51 mg/L,此时稻秆降解量也最多,半纤维素、纤维素和酸性洗涤木质素降解率分别为28.60%、47.32%和22.69%。研究表明,稻秆负荷与发酵pH通过影响稻秆半纤维素、纤维素和木质素的降解影响稻秆厌氧发酵产酸的进程和效果。     

醋酸纤维素包埋非水溶性介体催化强化生物反硝化特性

利用醋酸纤维素包埋法固定非水溶性醌类介体,研究其催化强化Paracoccus versutus菌株GW1的反硝化作用。结果表明,醌浓度在26.7 mmol/L时,固定化蒽醌(AQ)、1-氯蒽醌(1-AQ)、2-氯蒽醌(2-AQ)、1,5-二氯蒽醌(1,5-AQ)、1,8-二氯蒽醌(1,8-AQ)和1,4,5,8-四氯蒽醌(1,4,5,8-AQ)催化反硝化效率依次为:1,5-AQ1,8-AQ1,4,5,8-AQAQ1-AQ空白对照2-AQ。反应10 h时,1,5-AQ可使硝酸盐去除率比空白对照提高1.84倍;硝酸盐氮反硝化动力学拟合为零级反应,其速率常数Kx随1,5-AQ浓度的增加均呈线性增加(Kx=0.1885C1,5-AQ+8.378);水中溶解氧会降低GW1菌反硝化的效果;投加1,5-AQ的反硝化体系中亚硝酸盐积累的最大值比不投加介体的低48.3%;醋酸纤维素介体小球经过4次的重复利用,催化效果始终是空白对照的1.5倍以上。醋酸纤维素固定化非水溶性醌可以有效加速生物反硝化,表明其是一种较优的醌固定化方法,具有良好的应用价值。     

城市生活垃圾中可生化单基质的厌氧消化

在厌氧消化系统中,发酵细菌最主要的利用基质是淀粉、纤维素、脂肪和蛋白质等。本试验分别选取米饭、黄豆、芹菜和肥肉为上述四种基质的代表物质,通过对各物质进行的厌氧消化试验,探讨了它们的厌氧消化性能。结果表明。米饭在发酵初期降解速率最快,酸化也最明显。同时将消化初始阶段的pH控制在6．5时能使消化进入产甲烷阶段,没控制的只能停留在水解产酸阶段。将黄豆厌氧消化初期的pH控制在6．5并不能使消化顺利进行。将芹菜厌氧消化的初始pH值控制在6．5时可以加快它的降解速率。肥肉的厌氧消化也只有在对其消化进程控制pH值时才能顺利被降解。同时肥肉在厌氧消化进程中表现出了高产甲烷性能,产甲烷阶段累积产气量达13758mL,占总产气量的93．59％．     

Decomposition of carboxymethyl cellulose based on nano-knife principle

The traditional degradation of organic pollutants is based on the sacrifice of chemical or biological reagents. In this study, a purely physical technique was developed to break the chemical bonds and consequently decompose macromolecules in aqueous solution. Assisted with a high-speed mechanical blade, refined quartz sand grains with particularly sharp nanoscale edges can act as ‘nano-knives', which are able to cut the long chain of carboxymethyl cellulose(CMC, as a model molecule). High performance size exclusion chromatography measurements evidenced that the original CMC molecules(41,000 Da) were decomposed into a series of smaller molecules(460, 1000, 2200, 21,000, 27,000 and 31,000 Da). Consequently, the initial viscosity of the CMC solution(2 g/L) rapidly decreased by approximately 50% after 3 min treatment by the nano-knife materials along with the mechanical blade. Fourier transform infrared(FTIR) spectra indicated that the original functional groups were still present and new functional groups were not produced after shearing. The intensity of the main functional groupβ-1-4-glycosidic bond(wavenumber 1062 cm-1) was observed to markedly decrease after shearing. These results indicated that the long-chain CMC was cleaved into short-chain CMC. A degradation mechanism was proposed whereby the cutting force generated by the rapid motion of the nano-knives may be responsible for the breakage of β-1-4-glycosidic bonds in the macromolecular cellulose backbone. These results provide support for a potentially more affordable and environment-friendly strategy for physical-based decomposition of recalcitrant organic pollutants from aqueous solution without the need of chemical or biological reagents.     

Carboxymethyl cellulose thiol-imprinted polymers:Synthesis,characterization and selective Hg(Ⅱ) adsorption

Sulfur containing ion imprinted polymers(S-IIPs) were applied for the uptake of Hg(Ⅱ) from aqueous solution. Cysteamine which was used as the ligand for Hg(Ⅱ) complexation, was grafted along the epichlorohydrin crosslinked carboxylated carboxymethyl cellulose polymer chain through an amide reaction. The adsorption ability of S-IIPs towards Hg(Ⅱ)was investigated by kinetic and isotherm models, which, corresponding, showed that the adsorption process followed a pseudo-second-order, fitted well with the Langmuir isotherm with a maximum adsorption capacity of 80 mg/g. Moreover, thermodynamic studies indicated an endothermic and spontaneous reaction with the tendency of an enhanced randomness at the surface of the S-IIPs with temperature increases. S-IIPs indicated a high degree of selectivity towards Hg(Ⅱ) in the presence of Cu~(2+), Zn~(2+), Co~(2+), Pb~(2+)and Cd~(2+).Furthermore, the efficiency of S-IIPs was also evaluated against real samples showing86.78%, 91.88%, and 99.10% recovery for Hg(Ⅱ) wastewater, ground water and tap water,respectively. In this study, the adsorbent was successfully regenerated for five cycles, which allows for their reuse without significant loss of initial adsorption capability.     

Simple fabrication of carboxymethyl cellulose and κ-carrageenan composite aerogel with efficient performance in removal of fluoroquinolone antibiotics from water

● A composite aerogel was simply obtained to remove various fluoroquinolones (FQs). ● The structural and textural properties of this composite aerogel are improved. ● Its adsorption capacity was improved at a low content of coexisting Cu²⁺ or Fe³⁺ ion. ● Two substructural analogs of FQs are compared to explore the adsorption mechanisms. ● This aerogel after saturated adsorption can be reused directly for Cu²⁺ adsorption. 3D composite aerogels (CMC-CG) composed of carboxymethyl cellulose and κ-carrageenan were designed and fabricated using the one-pot synthesis technique. The optimized CMC-CG showed a good mechanical property and a high swelling ratio due to its superior textural properties with a proper chemically cross-linked interpenetrating network structure. CMC-CG was utilized for the removal of various fluoroquinolones (FQs) from water and exhibited high adsorption performance because of effective electrostatic attraction and hydrogen bonding interactions. Ciprofloxacin (CIP), a popular FQ, was used as the representative. The optimized CMC-CG had a theoretically maximal CIP uptake of approximately 1.271 mmol/g at the pH of 5.0. The adsorption capacity of CMC-CG was improved in the presence of some cations, Cu²⁺ and Fe³⁺ ions, at a low concentration through the bridging effect but was reduced at a high concentration. The investigation of adsorption mechanisms, based on the adsorption kinetics, isotherms and thermodynamic study, Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy analyses before and after adsorption, and changes in the adsorption performance of CMC-CG toward two molecular probes, further indicated that electrostatic attraction was the dominant interaction rather than hydrogen bonding in this adsorption. CMC-CG after saturated adsorption of CIP could be easily regenerated using a dilute NaCl aqueous solution and reused efficiently. Moreover, the disused aerogel could still be reused as a new adsorbent for effective adsorption of Cu²⁺ ion. Overall, this study suggested the promising applications of this composite aerogel as an eco-friendly, cost-effective, and recyclable adsorbent for the efficient removal of FQs from water.