纤维素的选择性氧化及发展趋势

纤维素是自然界取之不尽用之不竭的可再生资源,改变纤维素的结构,便赋予其许多新的功能。选择性氧化纤维素成为纤维素科学与纤维素基新材料研究领域中的热点。综述了纤维素的各种选择性氧化体系,重点介绍了TEMPO/NaClO/NaBr选择性氧化体系的反应条件、反应机理及最新的研究进展,并分析了氧化纤维素应用及发展前景。     

TEMPO催化氧化对球形再生纤维素气凝胶阳离子吸附性能的影响

采用2,2,6,6-四甲基哌啶-1-氧基自由基(TEMPO)选择性催化氧化体系对再生纤维素气凝胶进行表面羧基化改性,制备出羧基化的再生纤维素气凝胶。通过扫描电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)、紫外光谱和原子吸收等检测手段对不同氧化处理时间的纤维素气凝胶的微观形貌、化学结构和吸附性能进行表征分析,结果表明,随着氧化处理时间的增加,球形再生纤维素气凝胶的羧基含量逐渐增加,结构稳定性逐渐下降,在改性12h时可以获得羧基含量较高(1.25mmol/g)结构相对稳定的产品;TEMPO氧化处理增加了球形气凝胶表面的透过性,并且避免了内部网络因干燥和氢键缔合而产生的聚集;羧基的引入使球形纤维素气凝胶对阳离子染料和部分金属离子的吸附性能得到改善,其中对金胺O的最大吸附量为1.24mmol/g,对金属离子Cu2+的最大吸附量为0.55mmol/g。     

过氧化氢氧化制备羧基再生亚麻纤维素及其膨胀阻燃环氧树脂

采用过氧化氢制备羧基再生亚麻纤维素,通过红外光谱、核磁共振、X射线衍射和热重分析表征产物的结构与性能,研究表明再生亚麻纤维素上的C6伯羟基被选择性地氧化为羧基,而且氧化再生亚麻纤维素随着羧基含量的增加,其热稳定性下降。将其作为成炭剂,并与酸源、气源复配组成膨胀型阻燃剂(IFR)用于阻燃环氧树脂,通过极限氧指数测试(LOI)和垂直燃烧测试(UL-94)表征阻燃性能。研究表明,膨胀型阻燃剂的加入能有效地提高环氧树脂的阻燃性能。与EP/MFAPP/PER复合材料的LOI相比,EP/MFAPP/OLF27.4和EP/MFAPP/OLF34.5复合材料的LOI更高,MFAPP/OLF体系的阻燃效果比MFAPP/PER体系要好,这是因为MFAPP/OLF体系的催化成炭效果更好,样品表面生成的防护性炭层,起到了阻隔热量和氧气的作用并抑制了可燃性气体的释放。     

超声预处理提高蔗髓纤维素选择性氧化性能的研究

采用超声波对蔗髓纤维素进行预处理,研究超声条件对纤维素在4-乙酰氨基-2,2,6,6-四甲基哌啶氧自由基(4-AcNH-TEMPO)/次氯酸钠(NaClO)/亚氯酸钠(NaClO2)体系中的选择性氧化反应的影响。结果表明,超声预处理能显著提高纤维素的氧化反应活性,其中超声强度和时间对氧化纤维素性状影响较大,且在该体系中所得产物由水溶性和不溶性氧化纤维素构成。通过X射线衍射(XRD)、红外光谱(FT-IR)和扫描电镜(SEM)对超声前后的纤维素及其两种氧化产物进行了结构分析与表征。     

漆酶/TEMPO体系氧化棉纤维接枝壳聚糖制备抗菌纤维

利用漆酶/TEMPO体系选择性将纤维素C-6伯羟基氧化成醛基,得到单醛纤维素,再将壳聚糖通过席夫碱反应接枝到单醛纤维素上,制得接枝产物。将接枝产物进行红外光谱分析、SEM及能谱分析及壳聚糖含量的分析,确定接枝产物结构的变化和壳聚糖含量,并进一步对其抗菌性进行研究。结果表明,经漆酶/TEMPO体系氧化后,纤维素C-6伯羟基被选择性的氧化成醛基,与壳聚糖接枝反应后,壳聚糖的氨基与醛基反应生成CN;接枝产物表面出现了明显的变化且有壳聚糖存在;接枝产物中壳聚糖含量为4.55%;与棉纤维相比,接枝产物对大肠杆菌和金黄色葡萄球菌均具有抗菌性,且对大肠杆菌的抑制作用强于金黄色葡萄球菌。     

C6位氧化细菌纤维素的制备及结构表征EI北大核心CSCD

为了改善细菌纤维素的生物降解性,采用2,2,6,6-四甲基-1-哌啶酮(TEMPO)/Na Br/Na Cl O体系对细菌纤维素进行氧化,探讨了Na Cl O和TEMPO用量及反应时间对反应的影响,利用电导滴定、红外光谱、13C-核磁共振、X射线衍射和透射电子显微镜对固体产物进行了表征。结果显示,细菌纤维素取1 g,0.6 mol/L Na Cl O 8 m L,TEMPO 0.016 g,Na Br0.1 g,反应8 h可以获得羧基含量较高的氧化细菌纤维素(羧基含量为1.04 mol/kg)。红外光谱和13C-核磁共振波谱共同证明细菌纤维素C6位伯醇羟基被选择性催化氧化成了羧基,X射线衍射结果表明氧化后细菌纤维素的结晶结构没有发生明显改变,TEM结果显示氧化后细菌纤维素的纳米网状结构得到保留。利用TEMPO/Na Br/Na Cl O体系可以获得氧化度较高的微观结构无损伤的氧化型细菌纤维素。     

羟丙基纤维素的微观结构和溶解性及再生

基于碱性水性溶剂体系采用核磁共振谱、偏光显微镜和X射线多晶衍射仪等方法研究了羟丙基纤维素的微观结构、溶解性和再生特性。实验结果表明,在较低温度下,醚化物质的量取代度为0.19、黏均分子量约2.3万道尔顿的羟丙基纤维素在8%氢氧化钠、6%尿素和6%硫脲混合水溶液中显示良好的溶解性,室温干燥和高温干燥再生后的羟丙基纤维素都为纤维素Ⅱ型晶型;在较高温度下和不良溶剂体系中,未完全溶解的羟丙基纤维素在溶液中成棒状或片状结构,且伴随着高表观黏度,室温干燥和高温干燥再生后的羟丙基纤维素均存在纤维素Ⅰ型晶型。     

C6位选择性氧化竹浆纤维的制备与表征

通过HNO3/H3PO4-NaNO2体系选择性氧化制备了不同氧化程度的单羧基竹浆纤维素。研究了HNO3/H3PO4-NaNO2氧化条件对竹浆纤维的聚集态结构和物理力学性能的影响,利用红外光谱、扫描电镜、核磁共振碳谱及X射线衍射对氧化竹浆纤维的结构进行了表征。结果表明,竹浆纤维分子中的C6位伯羟基已被HNO3/H3PO4-NaNO2氧化体系选择性氧化为羧基,在FT-IR和13C-NMR谱图中明显出现了羧基特征峰。随着氧化剂用量的增加与氧化时间的延长,氧化竹浆纤维的失重率和羧基含量明显提高,但纤维的力学强度与结晶度逐渐降低。保持HNO3/H3PO4-NaNO2氧化时间在0 min~60 min范围内,氧化竹浆纤维的物理力学性能可满足纺织后加工及服用性能要求,且在竹浆纤维分子中引入了2.28%更具活性的羧基官能团,增强了氧化竹浆纤维进一步化学改性的能力。     

无机盐/离子液体对再生纤维素结构与性能的影响

合成了一种离子液体1-烯丙基-3-甲基咪唑亚磷酸甲酯盐([Amim][(MeO)PHO_2]),这种离子液体能很好地溶解纤维素,并加入与其阴离子结构类似的无机盐亚磷酸氢二钠(Na_2PHO_3)组成复合溶解体系。文中研究了离子液体和复合体系对纤维素结构与性能的影响,通过对原生和再生纤维素展开红外光谱、热重分析、X射线衍射及聚合度的测试表征,结果显示再生纤维素没有发生衍生化,但热稳定性和结晶度及聚合度均比原生纤维素低,且随着复合溶解体系中Na_2PHO_3含量的增大,从中再生出来的纤维素的聚合度越高、热降解温度越高、结晶度越低。这种结果可能是由于无机盐的加入降低了离子液体对纤维素的酸降解而导致的。     

C-6羧基氧化纤维素醋酸酯的制备和性能

以溶解级木浆作为原料,通过TEMPO（2,2,6,6四甲基哌啶1氧化物自由基）/NaClO/NaClO₂氧化体系对纤维素C-6羟基进行氧化,经过乙酰化处理后制备出C-6位含羧基的氧化纤维素醋酸酯。用红外光谱（IR）、X-射线衍射（XRD）和核磁共振（NMR）等手段表征了产物的结构,用热重分析（TGA）和差示扫描量热法（DSC）测试了产物的热性能。结果表明:所合成氧化纤维素醋酸酯的C-6位羧基取代度为0.15,乙酰基取代度为2.72（其中C 2为0.93、C-3为0.98、C 6为0.81）且取代均匀性较好;用C-6羟基的选择性氧化预处理可实现纤维素的可控酯化;产物能溶于DMSO（二甲基亚砜）;产物的晶型由纤维素Ⅰ型转变成纤维素Ⅱ型。氧化纤维素醋酸酯在185℃发生玻璃化转变,在257℃熔融。乙酰基的接入,使产物的热塑性提高。     

N-烯丙基吡啶氯盐离子液体/有机溶液复合溶剂对纤维素的溶解性能

采用一步法合成N-烯丙基吡啶氯盐离子液体([APy]Cl),用红外光谱(FT-IR)和核磁共振(1H-NMR)进行结构表征,并与常用有机溶液(二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)及吡啶)配成复合溶剂,测定并比较对棉浆粕的溶解能力。结果表明,四种复合溶剂均为纤维素的优良溶剂,其中在[APy]Cl/DMAc复合溶剂中溶解性能最佳,在100℃、DMAc质量分数为40%时,溶解度能达到12.25%。利用FT-IR、X射线衍射(XRD)和热重分析(TGA)对溶解再生前后纤维素膜的结构进行分析。结果表明,四种复合溶剂均为纤维素的直接溶剂,可将晶型由Ⅰ转变成Ⅱ,热稳定性良好。     

TEMPO氧化纤维素纳米纤丝对多壁碳纳米管分散性的影响

以竹粉为原料,采用2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）氧化法通过改变NaClO的添加量制备出不同羧基含量及形态的纤维素纳米纤丝（CNFs）,并将制备的CNFs作为分散剂对多壁碳纳米管（MWCNTs）进行分散处理,得到不同分散浓度的CNFs/MWCNTs悬浮液,采用Beer-Lambert定律对MWCNTs的分散量进行测定,并采用原子力显微镜（AFM）、激光粒度分析仪（LPSA）等手段评价了不同羧基含量及形态的CNFs对MWCNTs的分散效果。结果表明:随着NaClO添加量的增加,CNFs的横截面直径逐渐变小,羧基含量逐渐增加,同时,CNFs对MWCNTs的分散量逐渐增大;当CNFs的羧基含量从0.635 mmol/g增加到1.646 mmol/g时,对MWCNTs的分散量从19%增加到39%;不同CNFs/MWCNTs悬浮液中的粒度分布系数（PDI）值均小于0.3,且不同悬浮液的Zeta电位绝对值均高于30 mV,表明不同羧基含量的CNFs均能对MWCNTs有较好的分散效果;同时,随着羧基含量的增加,CNFs对MWCNTs的分散效果越好,CNFs/MWCNTs复合薄膜的抗拉应力逐渐增大,而且电阻率逐渐降低,当CNFs羧基含量为1.646 mmol/L时,CNFs/MWCNTs复合薄膜抗拉应力达到了91 MPa,薄膜电阻率低至0.1460 Ωcm。      

Degradation of 2,4-dinitrophenol by combining sonolysis and different additives.

Based on the effects of various additives on ultrasonic degradation of 2,4-dinitrophenol (DNP) in aqueous solution, the degradation mechanisms and reaction kinetics of DNP in different processes were proposed. The results showed that some additives, such as CuO, CCl(4), O(3), NaCl and KI, were favorable for DNP sonochemical degradation. On the contrary, DNP degradation efficiency was restrained by Na(2)CO(3), indicating that OH radicals oxidation played an important role in DNP ultrasonic removal. The significant increases in DNP degradation in US/CuO/H(2)O(2), US/CCl(4) and US/O(3) systems were also related to the intermediates formed during the reactions, such as HO(2)/O(2)(-) radicals, chlorine-containing radicals and HClO. In addition, DNP ultrasonic removal was observed to behave as pseudo-first-order kinetics under different experimental conditions tested in the present work.     

磷酸酯类离子液体对纤维素溶解性能的研究

采用一步法合成了两种磷酸酯类离子液体:1,3-二甲基咪唑磷酸二甲酯盐([MMIM]DMP)和1-乙基-3-甲基咪唑磷酸二乙酯盐([EMIM]DEP),并比较了它们对纤维素的溶解性能。结果表明,两种离子液体均能在一定条件下溶解纤维素,而[EMIM]DEP表现出较优的溶解能力,再生得到纤维素膜;随着溶解温度的升高,溶解时间缩短。采用红外光谱(FT-IR)、热重失重(TGA)分析、X射线衍射(XRD)、扫描电镜(SEM)等对再生前后的纤维素进行了表征。结果表明,未经活化的纤维素可直接溶于离子液体中而不发生其它衍生化反应;溶解再生后的纤维素晶型发生变化;经[EMIM]DEP溶解再生后纤维素热稳定性和聚合度下降较小,再生纤维素膜结构致密均一。     

Mucoadhesive nano-sized supramolecular assemblies for improved pre-corneal drug residence time

Abstract

Context: Mucoadhesive nanoparticles were compared with non-aggregated constituent polymers for effect on pre-corneal residence of dexamethasone phosphate (DP) or met-enkephalin (ME), administered by eye-drops to rabbits.

Objective: Deepening the knowledge of ophthalmic nanoparticulate systems in terms of ability to prolong pre-corneal residence.

Materials and methods: Medicated nanoparticles resulted from gelation of quaternary ammonium–chitosan conjugate or its thiolated derivative with hyaluronan in the presence of drug. Particles were analyzed by light scattering. Dialysis removed non-encapsulated drug, dynamic dialysis measured drug–polymer interactions, and lyophilization-stabilized product. Dispersions were regenerated from lyophilized products. Also solutions of non-thiolated or thiolated chitosan derivative were administered. Mean drug residence time (MRT) in tears was determined by collecting samples from lower marginal tear strip of albino rabbits using capillaries.

Results and discussion: Nanoparticle size of regenerated dispersions was 400–430?nm (DP-systems), 360–370?nm (ME-systems); the drug content was 2.5?mg/mL (DP) or 0.3?mg/mL (ME). The MRT for DP nanoparticles from non-thiolated derivative was higher than that for non-aggregated polymer, due to stronger concurrent interactions of positively charged nanoparticles with ocular surface and drug. Thiolated polymer nanoparticles and non-aggregated parent polymer, both interacting weakly with DP, showed similar MRT values. The MRT of ME could only be enhanced by protecting drug from enzymatic hydrolysis. This was done by nanoparticle systems, whereas non-aggregated polymers were ineffective.

Conclusion: Developing a nanoparticle system rather than a solution of mucoadhesive polymer, for prolonging pre-corneal residence, is convenient, provided nanoparticles interact strongly with both ocular surface and drug, or protect drug from metabolic degradation.     

Stationary-state oxidized platinum microsensor for selective and on-line monitoring of nitric oxide in biological preparations

Despite the multifaceted biomedical significance of NO, little progress has been achieved so far in the quantitative understanding of the signal transduction mechanisms where NO is involved. To help progress in this area, we propose a simple electrochemical NO sensor here, consisting of a glass sealed platinum microdisk electrode coated with cellulose acetate to reduce both surface fouling by proteins and response to potential interferences. A differential amperometry protocol is optimized to improve selectivity and provide a stationary oxidation state of the platinum surface, which prevents loss in sensitivity during long-term use. We found the oxidation of NO by O2 second order in [NO] with a rate constant of (8.0 +/- 0.4) x 10(6) M(-2) s(-1), in good agreement with literature data obtained by other than electrochemical methods. The release rates of NO detected in cultures of activated macrophages were on the order of 20 pmol/ (10(6)cells s) and correlated well with the nitrite content determined by the spectrophotometric Griess assay.     

Assessment of a new carbon tetrachloride destruction system based on a microwave plasma torch operating at atmospheric pressure

A new system for destroying volatile organic waste based on a microwave plasma torch that operates at atmospheric pressure and is coupled to a reactor affording isolation of output gases and adjustment of the plasma discharge atmosphere is proposed. The system was assessed by using carbon tetrachloride as the target volatile organic compound (VOC) and argon as the main gas in a helium atmosphere. Under optimal conditions, a microwave power of less than 1000 W was found to reduce the CCl(4) concentration at the reactor outlet to the parts-per-billion level and hence to virtually completely destroy the VOC. With high argon flow-rates and CCl(4) concentrations, the energy efficiency can reach levels in excess of 3000 g/kWh. Output gases and species in the plasma, which were identified by gas chromatography and light emission spectroscopy, respectively, were found to include no halogen-containing derivatives resulting from the potential cleavage of CCl(4). In fact, the main gaseous byproducts obtained were CO(2), NO and N(2)O, in addition to small traces of Cl(2), and the solid byproducts Cl(2)Cu and various derivatives depending on the particular reactor zone.     

Characterization and activity of Pd-modified TiO2 catalysts for photocatalytic oxidation of NO in gas phase

Pd-modified TiO(2) prepared by thermal impregnation method was used in this study for photocatalytic oxidation of NO in gas phase. The physico-chemical properties of Pd/TiO(2) catalysts were characterized by X-ray diffraction analysis (XRD), Brunauer-Emmett-Teller measurements (BET), X-ray photoelectron spectrum analysis (XPS), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), UV-vis diffuse reflectance spectra (UV-vis DRS) and photoluminescence spectra (PL). It was found that Pd dopant existed as PdO particles in as-prepared photocatalysts. The results of PL spectra indicated that the photogenerated electrons and holes were efficiently separated after Pd doping. During in situ XPS study, it was found that the content of hydroxyl groups on the surface of Pd/TiO(2) increased when the catalyst was irradiated by UV light, which could result in the improvement of photocatalytic activity. The activity test showed that the optimum Pd dopant content was 0.05 wt.%. And the maximum conversion of NO was about 72% higher than that of P25 when the initial concentration of NO was 200 ppm, which showed that Pd/TiO(2) photocatalysts could be potentially applied to oxidize higher concentration of NO.