氟吗啉合成工艺热危险性及动力学研究

氟吗啉是一种新型杀菌剂, 合成工艺热危险性和动力学研究将解决工程问题, 并保障安全生产. 采用差示扫描量热-热重分析仪(DSC-TG)测试主要原料、中间体和产品的热稳定性, 采用反应量热仪(RC1)研究反应热行为, 同时开展反应动力学研究. 研究结果显示, 主要中间体(3,4-二甲氧基苯基)(4-氟苯基)甲酮吸热分解温度为559.3 K, 乙酰吗啉吸热分解温度为478.2 K, 氟吗啉吸热分解温度为638.6 K. 氟吗啉合成反应摩尔放热量为15.44 kJ/mol, 绝热温升ΔT_ad为9.1 K, 本研究合成工艺的热危险性较小. 氟吗啉合成反应动力学方程为：r_A=kc_A^a=8.34×10^-3C_A^0.57, 对主要中间体(3,4-二甲氧基苯基)(4-氟苯基)甲酮的反应级数为0.57 级.     

新型杀菌剂氟吗啉在黄瓜植株体内的吸收传导行为

利用生物测定技术和高效液相色谱法研究了氟吗啉在黄瓜植株体内的吸收、传导和分布行为及其机制. 结果表明, 氟吗啉能被黄瓜植株被动吸收, 并通过木质部在体内传导和分布.     

植物细胞壁纳米结构与纳米纤维素的化学纯化处理结合机械解纤法制备

植物中含有自然界中储量最为丰富的天然高分子—纤维素.植物具有多层级结构,在微观层面由细胞构成.细胞的主体物质存在于细胞壁中,主要以纤维素纳米纤丝—基体复合结构形式存在,这种结构对植物的性能和功能起到了至关重要的作用.采用化学纯化处理结合机械解纤策略,可以将细胞壁内部起支撑作用的纳米纤维素解离出来.纳米纤维素展现出一维纳米纤维结构、高结晶度以及优异的力学性能和热性能,在许多领域均展现出巨大的应用潜力.本文主要介绍我们课题组近几年对植物多层级结构、细胞特征、细胞壁生物合成以及细胞壁纳米结构的研究和思考,总结了在植物纳米纤维素化学纯化处理结合机械解纤法制备方面的研究进展,并对其存在的问题以及今后重点研究方向进行了总结和展望.     

海带细胞壁及细胞壁多糖中Sr,Ca,Mg,P分布

对海带细胞壁及细胞壁中的藻酸盐、褐藻糖胶、纤维素等多糖类物质中的Ｓｒ、Ｃａ、Ｍｇ、Ｐ含量作了ＩＣＰ－ＡＥＳ测定。结果显示，海带中的锶主要位于细胞壁，细胞壁中的锶主要位于揭藻糖胶。     

植物细胞壁蛋白与木质纤维素酶解

木质纤维素是生产生物能源和材料的重要原料.木质纤维素具有高度复杂的结构,其酶解效率除了受自身的凝聚态结构影响外,还受到细胞壁自身组分的影响.本文综述了植物细胞壁中主要蛋白的特征及其与木质纤维素酶解的关系.从植物自身细胞壁蛋白活性出发来研究木质纤维素的酶解,为研究其酶解机制和高效酶解方法提供了新思路.     

用TEAOH-C4H9NO复合模板剂合成SAPO-34分子筛的研究Ⅰ.SAPO-34分子筛的合成与表征

 以吗啉(C4H9NO)为主要模板剂,以少量四乙基氢氧化铵(TEAOH)为辅助模板剂合成了SAPO -34分子筛,并采用X射线衍射、扫描电镜、傅里叶变换红外光谱和热重-差热分析等手段对 合成的SAPO-34分子筛进行了表征. 结果表明,TEAOH在导向生成SAPO-34分子筛骨架过程中 表现活跃,占据了较多的平衡骨架负电荷的位置,而吗啉主要起到填充分子筛孔道的作用. 用 TEAOH-C4H9NO复合模板剂合成的SAPO-34分子筛,其晶粒远小于单用吗啉模板剂合成的 分子筛.     

改进的QuEChERS-气相色谱-质谱联用法测定蔬菜中的氟吗啉和烯酰吗啉残留

建立了同时测定蔬菜中氟吗啉和烯酰吗啉残留的改进的QuEChERS-气相色谱-质谱（GC-MS）联用法。前处理过程以乙腈高速匀浆提取样品,应用改进的QuEChERS方法对样品进行提取、盐析和净化,并采用气相色谱-质谱联用仪在选择离子监测（SIM）模式下测定了多种蔬菜中的氟吗啉和烯酰吗啉残留量,以基质匹配标准溶液外标法定量。选用DB-5 MS石英毛细管柱（30 m×0.25 mm×0.25 μm）,流速1.1 mL/min,采用电子轰击电离源,选择监测离子氟吗啉为m/z 285、371、165;烯酰吗啉为m/z 301、387、165。结果表明：在优化条件下,氟吗啉和烯酰吗啉在10~1000 μg/kg范围内线性关系良好,相关系数不低于0.999,不同基质中的检出限（S/N=3）范围为0.67~2.42 μg/kg。对于生姜、番茄、胡萝卜、菠菜、甘蓝和白木耳空白样品,在10、20、100 μg/kg共3个水平下氟吗啉和烯酰吗啉的加标回收率为71%~116%,相对标准偏差（RSD）为1.8%~14.7%。同时,本研究对蔬菜中氟吗啉和烯酰吗啉残留检测的裂解机理和基质效应进行了考察。本方法具有操作简便、快速、准确的特点,可用于蔬菜中氟吗啉和烯酰吗啉残留量的日常检测。     

高效液相色谱法检测氟吗啉在土壤中的降解

建立了氟吗啉在土壤中残留分析的高效液相色谱(HPLC)检测方法,在实验室条件下对氟吗啉在我国具有代表性的3种土壤中的降解动态进行了研究。样品通过V(正己烷)∶V(乙酸乙酯)=1∶2混和溶液萃取,经弗罗里硅土SPE柱净化,浓缩后进行HPLC检测。结果表明,药剂土壤添加浓度在0.2和2.0mg/kg时,氟吗啉在不同土壤中回收率为78.8%～97.1%;标准偏差为2.24%～7.48%。氟吗啉在土壤中的降解遵循一级动力学方程;氟吗啉在3种土壤中的降解速率大小依次为黑龙江黑土>江西红土>河南黄土,其降解半衰期分别为99.02、106.64和157.53d,降解速率常数(k)分别为7.0×10-3、6.5×10-3和4.4×10-3。根据国内农药在土壤中的残留划分标准,氟吗啉属于中等降解类农药。比较氟吗啉在非灭菌与灭菌的黑龙江黑土、江西红土和河南黄土中的降解情况表明,药剂在非灭菌土中降解明显快,分析可能是土壤中微生物对氟吗啉的降解具有显著的影响。     

新型催化剂钛硅中空微球催化氧化N-甲基吗啉

N-甲基氧化吗啉(NMMO)是纤维素的优良溶剂,本文首次以合成的具有中空结构的钛硅微球作为催化剂,以双氧水为氧化剂,将N-甲基吗啉氧化为NMMO的新工艺,考查了原料配比、反应温度、反应时间、催化剂钛硅含量等实验条件对产率的影响.用SEM、IR、TEM等手段对催化剂的形貌及结构进行了表征;得出的最佳工艺条件是:反应最佳温度为70℃,原料最佳质量配比为1.30∶1.61(N-甲基吗啉∶双氧水),反应时间6小时,选用含钛量5%的钛硅中空微球作催化剂,产率达到89%.     

植物细胞壁蛋白与木质纤维素酶解

木质纤维素是生产生物能源和材料的重要原料。木质纤维素具有高度复杂的结构,其酶解效率除了受自身的凝聚态结构影响外,还受到细胞壁自身组分的影响。本文综述了植物细胞壁中主要蛋白的特征及其与木质纤维素酶解的关系。从植物自身细胞壁蛋白活性出发来研究木质纤维素的酶解,为研究其酶解机制和高效酶解方法提供了新思路。     

Chiral nematic phase formation by aqueous suspensions of cellulose nanocrystals prepared by oxidation with ammonium persulfate

There is continuing interest in the growing family of nanocellulosic materials prepared from plant cell wall material. While most of the research on cellulose nanocrystals has focused on the product of sulfuric acid hydrolysis stabilized by surface sulfate half-esters, cellulose nanocrystals with surface carboxyl groups have also been prepared by oxidation of lignocellulosic materials with ammonium persulfate. The major difference is that the persulfate oxidation leads to nanocrystals stabilized by surface carboxyl groups. Some properties of cellulose nanocrystals from cotton and wood, prepared by persulfate oxidation, are compared with those observed for nanocrystals prepared by sulfuric acid hydrolysis. Evidence from polarized light microscopy showed that the nanocrystal suspensions prepared by persulfate oxidation also form chiral nematic ordered phases in water.     

Cool temperature hinders flux from glucose to sucrose during cellulose synthesis in secondary wall stage cotton fibers

Current knowledge about the integration of cellulose synthesis into cellular carbon metabolism and the cool temperature sensitivity of cellulose synthesis is reviewed briefly. Roles for sucrose synthase (to channel UDP-glucose to the cellulose synthase) and sucrose phosphate synthase (to recycle the fructose released by sucrose synthase to more sucrose) in secondary wall cellulose synthesis are described. Data are presented that implicate sucrose synthesis within cotton fibers as a particularly cool temperature-sensitive step in the partitioning of carbon to cellulose. Sugar metabolism during fiber secondary wall deposition was analyzed in in vitro cultures of ovules from two cultivars of Gossypium hirsutum L. (cv. Acala SJ-1 and cv. Paymaster HS 200), which had different levels of cool temperature sensitivity. The sizes of the sucrose, glucose, and fructose pools within fibers at 4 and 7 h after a temperature shift to 15 or 34 °C did not change in either cultivar. Feeding exogenous U-¹⁴C-glucose in pulse and pulse/chase experiments showed that uptake of glucose and transport through the ovule into fibers occurred at the same rate at 34 and 15 °C. In contrast, the flux from glucose to sucrose within fibers was greatly hindered at 15 °C in both cultivars. Since sucrose is the preferred donor of UDP-Glc to the cellulose synthase during secondary wall deposition, this sensitivity in sucrose synthesis is likely to at least partially explain the cool temperature sensitivity of cotton fiber cellulose synthesis that is observed in the field.     

Mercerization and acid hydrolysis of bacterial cellulose

Structural changes in never- dried, disintegrated bacteria l cellulose by treatment with aqueous NaOH were examined by electron microscopy, X-ray diffractometry and acid hydrolysis behaviour and compared with those of cotton cellulose. The microfibril kept its fibrillar morphology after treatment with NaOH solutions of less than 9% (w/w), but changed into irregular aggregates when treated with NaOH above 12% (w/w), corresponding to the crystal conversion to cellulose II. The crystallinity of the resulting cellulose II was very low after a brief alkali treatment, but was increased significantly by elongated treatment (up to 10 days). In contrast, cotton cellulose was converted to cellulose II of fairly high crystallinity by alkali treatment of as little as 3 min duration, and the crystallinity did not change with longer treatments. The leveling-off degree of polymerization (LODP) of bacterial cellulose was decreased from 150 to 50 by 18% (w/w) NaOH treatment, while that of cotton linter decreased from 260 to 70. These characteristic differences between cotton linter cellulose and bacterial cellulose can be ascribed to a basic difference in microfibrillar organization in these materials: the microfibrils in cotton cellulose are in close contact with neighbouring microfibrils having opposite polarity, and in bacterial cellulose are isolated from each other and require chain folding to form the antiparallel cellulose II crystal     

THE EFFECT OF CHRONIC APPLICATIONS OF TRETINOIN(RETINOIC ACID) ON ACUTE RESPONSES OF MAMMALIAN SKIN TO UVB RADIATION IN VIVO

Abstract The effects of long—term applications of tretinoin(retinoic acid; RA) on acute responses to UVB radiation were examined in hairless mouse skin in vivo. The skin was examined histologically and the radioactive tracer [³H]-thymidine was used to study premitotic semiconservative DNA synthesis in the epidermal basal cells. Ten and 23 wk applications of a 0.05% RA solution (3 times a wk) induced epidermal acanthosis, hypertrophy of the individual cells and an increased number of [³H]-thymidine-labelled basal cells. At both time periods there was a distinct reduction in the expected inhibition of DNA synthesis at 4 h and the expected acceleration of DNA synthesis at 48 h after a single exposure to UVB radiation. In addition, the histologic morphology was unchanged at 48 h post irradiation. Thus, the repeated RA applications had a definitive influence on at least two aspects of the cutaneous response to UVB energy.     

“Osmiophilic particles”—a fungal agent with characteristic distribution in white-and brown-rotted wood

When pine wood decayed by white- and brown-rot fungi was observed in TEM after fixation and staining with glutaraldehyde/osmium tetroxide/ uranylacetate and embedding in Spurr’s ultralow viscosity resin electron dense particles, called “osmiophilic particles,” a typical distribution for the two decay types could be observed: in white-rotted wood the particles could be found in and around the hyphae and on the lumen surface of the wood cell wall, mostly aggregated to thick clusters. During the whole course of decay the wood cell walls were free of the particles, but they were present on the corroded surfaces. In brown-rotted wood the “osmiophilic particles” also could be found in and around the hyphae, but in contrast the particles were distributed over all the wood cell wall layers from the early to late stages of decay. The distribution of the “osmiophilic particles” coincides with the place where the major cell wall degradation takes place: in white-rot the cell walls are degraded from the lumen to the middle lamella; in brown-rot a depolymerization and degradation of the carbohydrates takes place all over the wood cell wall. Since the “osmiophilic particles” can be found where the degradation takes place, it can be concluded that they are causally connected with wood decay. The fact that they also were found in, and some of them also around, hyphae grown on malt-agar or Sabouraud-dextrose-agar proves that they are produced by the fungi and cannot be degradation products. The possibility that they could be preparative artifacts can be excluded because uncolonized wood was free of “osmiophilic particles.” Since the “osmiophilic particles” are produced by the fungi and can be found in places where wood is decaying, it can be further concluded that they are a fungal agent that is involved in wood degradation, probably fungal enzymes. The observation that the large “osmiophilic particles,” which may have a size of up to 20 nm, are composed of globular subunits of a diameter of 2—3 nm also speaks for their enzymatic nature. To find out which type of enzyme they might be, the white-rot fungusTrametes hirsuta was grown on wood pulp with 7% lignin, on delignified wood pulp containing cellulose and hemicellulose, and on filterpaper (pure cellulose). The hyphae on wood pulp containing 7% lignin were surrounded by thick sheaths of “osmiophilic particles,” whereas with the hyphae grown on delignified wood pulp and pure cellulose only a few particles could be found. This makes it clear that the production of the “osmiophilic particles” is induced by lignin.     

Effects of mechanical stretching on average orientation of cellulose and pectin in onion epidermis cell wall: A polarized FT-IR study

The organization of polysaccharides in plant cell walls is important for the mechanics of plant cells. Spectral analysis of cell walls by polarized IR can reveal polysaccharide organization, but may be complicated by dipoles not aligned with the backbone. For instance, analysis of uniaxially-aligned cellulose Iβ film revealed that the dipole transition vector of the 1160 cm^?1 band involving stretch vibrations of glycosidic C1–O–C4 linkages is approximately at 30° with respect to the backbone of the cellulose chain, because of coupling with C5–O–C1 bonds in the six-membered rings. In the case of homogalacturonan, the dipole transition vector of the ester carbonyl group vibration (ν_C=O, 1745 cm^?1) is expected to be nearly normal to the homogalacturonan backbone. Using this information and the dichroism equation, the change in net orientation of cell wall polymers upon mechanical stretch was determined by polarized IR analysis. Never-dried abaxial outer epidermal cell walls of the second scale of onion bulb were mechanically stretched along longitudinal or transverse directions with respect to the long axis of the cells and then dried while under mechanical stretch. The average orientations of both 1160 and 1745 cm^?1 vibration transition dipoles were rotated by ~5° and ~4°, respectively, along the stretch direction from their initial random distributions upon longitudinal strain by 14%; and by ~4° and ~3°, respectively, upon transverse strain by 12%. These results imply that both cellulose microfibrils and pectins in the cell wall are passively realigned along the stretch direction by external mechanical force. The analytical methodology developed here will be useful to study how cell wall polymers might reorganize during cell wall growth and development.     

Highly specific capacitance materials constructed via in situ synthesis of polyaniline in a cellulose matrix for supercapacitors

On the basis of the requirements for both biobased economy and energy storage materials, we are interested in using cellulose-based microporous film as a template for in situ synthesis of polyaniline (PANI). Multifunctional carbon nanotube (CNT)/cellulose composite films were also prepared from a CNT/cellulose suspension in a NaOH/urea aqueous system. Subsequently, PANI was synthesized in situ in the pores of cellulose and CNT/cellulose substrates to construct PANI/cellulose (PC) films and PANI/CNT/cellulose (PCC) films, respectively. Both PC and PCC films were flexible and exhibited a highly specific capacitance and good cycle stability. With the addition of CNTs, the specific capacitance of the PCC films as supercapacitor materials was significantly improved. Moreover, a homogeneous structure intertwined with the cellulose, CNTs and PANI appeared in the composite films, indicating good miscibility. This work has provided a new approach to the fabrication of flexible, lightweight, highly effective, and low-cost energy storage materials, broadening the applications of cellulose.     

Spiral structures of cotton fiber

In the present article, data from the microscopic investigation of the morphological structure of a cellular wall and plasmalemma of the Central Asian cotton fiber are given at different stages of their development. The objects under investigation were live hairs of five middle-fiber cotton species (Tashkent-1, 108-F, Namangan-77, Margelan-3, G. llirsutum L.) and the coarse-fiber variety of G. arboreum L., so-called Turfan Gtiza. To observe the cotton hair surface morphology, the original method of gelatinous prints was used. It is shown that, in all investigated samples of cotton cell-hairs, spiral structures are observed in the packing of cellulose microfibrils on the surface of the primary cell wall. Also, it is established that the plasmalemma of a cotton cell-hair makes a spiral movement along the direction of its growth. On the basis of the received data, a conclusion is made about the spiral mechanism for the deposition of cellulose microfibrils on a primary cell wall surface and the spiral movement of plasmalemma.     

Antifungal cellulose by capsaicin grafting

Cellulose is one of the most abundant materials in nature. Besides its biological function, cellulose can be extracted from the cell wall and used in several industrial applications. Thus, it can be used in papers, pharmaceuticals, food, cosmetics and innovative materials such as nanocomposites, packaging, coatings and dispersion technology. With the aim of extending cellulose applications and producing so-called “smart” materials, new functionality can be introduced by physical or chemical modifications. Taking into account that capsaicin, the active component of chili peppers, is an excellent antifungal agent, a potential new material could be obtained by chemical reaction between this active compound and cellulose. In this work, capsaicin grafting onto cellulose using polycarboxylic acid as linking agent is proposed. The reaction occurrence was corroborated by Fourier transform infrared spectroscopy and UV–Vis spectrophotometry in reflectance mode. Modified cellulose with <2 wt% of capsaicin shows a strong change in antifungal activity with respect to the unmodified one. This activity was evaluated by the fungal growth inhibition test with two different fungi, Trametes versicolor and Gloeophyllum trabeum. Modified cellulose samples showed a high percentage of fungal growth inhibition, demonstrating the success of the cellulose modification and high antifungal power of the grafting molecule.     

The mechanism and regulation of cellulose synthesis in primary walls: lessons from cellulose-deficient Arabidopsis mutants

Cellulose-deficient Arabidopsis mutants were identified using FT-IR microspectroscopy. The study of these mutants not only led to the identification of actors in cellulose synthesis, but also provided insights in the organization of the hexameric terminal complex from CESA mutants and identified unsuspected accessory proteins with so far unknown roles in the synthesis and/or assembly of cellulose microfibrils. Finally, mutant analysis established a role for protein glycosylation in cellulose synthesis and provided new perspectives on the developmental regulation of cell wall synthesis and the role that cellulose synthesis plays in the control of cell elongation.