白腐菌选择性降解木质素的研究

对15株白腐真菌进行了以玉米秸秆为基质的初步筛选，从中获得一株选择性系数较高的菌株Y10，并对其降解玉米秸秆的情况进行了研究。结果表明，在30天的培养过程中菌株Y10对玉米秸秆降解的选择性系数都大于1，第15天选择性系数最高为3.88。对未经降解和降解过的玉米秸秆分别作了紫外光谱和红外光谱分析，结果表明，经该菌降解后玉米秸秆的化学成分发生了很大变化，且木质素的降解程度要大于纤维素的降解程度。对菌株Y10进行了ITS-5.8S rDNA序列鉴定，初步判定其为Cerrena sp.。 为了考查不同的外源添加物对菌株Y10降解玉米秸秆的影响，在以玉米秸秆为基质的固态发酵培养基中分别添加了7种金属离子、8种碳源、6种氮源。结果显示，这7种金属离子均能促进木质素的降解，并且一定浓度的某些离子明显抑制纤维素的降解；其中添加0.036%的MnSO4·H2O和0.36%的MgSO4·7H2O对纤维素降解的抑制作用比较强，降解率分别为0.96%和1.31%，木质素的选择性系数分别达到了34.40和20.17。8种碳源中除麦芽糖外都能促进木质素的降解，除微晶纤维素外都明显促进纤维素的降解。6种氮源中酒石酸铵、硫酸铵、草酸铵和氯化铵的添加都会使该菌生长变慢，而且氮源浓度越高菌丝生长越慢。外加碳源和金属离子对半纤维素降解和选择性系数的影响不大。 同时对菌株Y10在液态培养下产木质素降解酶的条件和培养基做了优化。结果表明，在初始产酶培养基中，菌株Y10的漆酶酶活在第10d达到最高，锰过氧化物酶酶活在第11d达到最高，基本上检测不到木质素过氧化物酶。菌株Y10产漆酶的最适温度为32℃，最适PH为6.0；产锰过氧化物酶的最适温度为32℃，最适PH为6.5。菌株Y10产漆酶的最佳碳源为甘露糖，最佳氮源为酒石酸铵，最适诱导剂VA浓度为3 mmol/L，最适表面活性剂TW-80浓度为1%。 利用响应面法对其产漆酶的培养基进行优化，优化后的培养基配方为葡萄糖10.00 g/L，酒石酸铵0.50 g/L，大量元素296.50 ml/L，微量元素100.00 ml/L，NTA 1.40 g/L，VA 5.00 mmol/L，吐温-80加入量为0.10%。进行了菌株Y10产漆酶的验证实验，实测酶活为5282.56 U/L，与预测酶活5162.73 U/L接近。在优化后培养基中，菌株Y10在第14 d达到生长的最高峰，第20 d时，漆酶酶活最高，为11325.00 U/L；第16 d时，锰过氧化物酶酶活最高，为30.77 U/L。 对菌株Y10的漆酶酶学性质做了初步的研究，结果显示，酶反应的最适温度为40℃-65℃，最适PH为3.0。在40℃，PH=3.0时，漆酶催化ABTS反应的米氏方程为 。 Fifteen white-rot fungi based on corn stalk were screened. One white-rot fungus Y10 with high selectivity value was obtained. The degradation of corn stalk was initially studied. The results indicated that the selectivity value was above 1 during the 30 day-cultivation and the highest was 3.88 after 15 days. The composition of untreated and treated stalk was analyzed through ultraviolet spectroscopy and infrared spectroscopy. It was found that the composition of treated stalk was greatly altered and the degree of the degradation of lignin is greater than the cellulose. Y10 was identified as Cerrena sp. by ITS -5.8S rDNA sequence analysis. The influence of metal ions, carbon sources and nitrogen sources on corn stalk degradation by white-rot fungus was studied. While all seven metal ions could promote lignin degradation, the cellulose degradation was best inhibited at certain ion concentrations. Notably, when 0.036% MnSO4·H2O and 0.36% MgSO4·7H2O were added into the medium, the cellulose degradation was restrained to the extents that the coefficients of lignin selectivity rose to 34.40 and 20.17 respectively. It was also found that all carbon sources except maltose can promote lignin degradation. The addition of carbon sources other than microcrystalline cellulose significantly promoted cellulose degradation. The addition of the nitrogen sources, ammonium tartrate, ammonium sulfate, oxalate, ammonium chloride, resulted in remarkable inhibition to mycelium growth; the larger the concentrations of nitrogen sources are, the slower the mycelium grew. The addition of carbon sources and metal ions had less impact on the degradation of hemicellulose and selectivity value. Meanwhile, we optimized the conditions and culture medium of the lignin-degrading enzyme production of strain Y10. The results showed that in the initial culture medium, the Lac activity was highest at the 10th day, the MnP activity was highest at the 11th day and the LiP could not be detected. The optimum condition of Lac was at temperature 32 and PH =6.0 and the optimum condition of MnP was at temperature 32 and PH =6.5. The optimum carbon source for Lac was seminose, the optimum nitrogen source was ammonium tartrate, the optimum content of VA was 3 mmol/L, the optimum content of TW-80 was 1%. PB and RSM were used to optimize the culture medium of laccase by white-rot fungus Y10. The optimum culture medium was consist of glucose 10.00 g/L, ammonium tartrate 0.50 g/L, macro elements 296.50 ml/L, trace elements 100.00 ml/L, NTA 1.40 g/L, VA 5.00 mmol/L, TW-80 0.10%. Under the optimal conditions, the activity of laccase was 5282.56 U/L and the experimental value agreed with the predicted value 5162.73 U/L. The biomass was highest at the 14th day, the Lac activity was highest at the 20th day, the MnP activity was highest at the 16th day. The results of the studies on the characteristics of Lac showed that the optimum temperature for Lac activity is 40℃-65℃ ; the optimum PH for Lac activity is 3.0 and under 40℃，PH=3.0, the Michaelis-menten equation of Lac catalized ABTS oxidation was .

AgBiVMo oxide catalytic membrane for selective oxidation of propane to acrolein

A metal ions (Ag, Bi, V, Mo) modified sol-gel method was used to prepare a mesoporous Ag0.01Bi0.85V0.54Mo0.45O4 catalytic membrane which was used in the selective oxidation of propane to acrolein. By optimizing the preparation parameters, a thin and perfect catalytically active membrane was successfully prepared. SEM results showed that the membrane thickness is similar to5 mum. XRD results revealed that Ag0.01Bi0.85V0.54Mo0.45O4 with a Scheelite structure, which is catalytically active for the selective oxidation of propane to acrolein, was formed in the catalytic membrane only when AgBiVMoO concentrations were higher than 40%. Catalytic reaction results demonstrated that the selective oxidation of propane could be controlled to a certain degree, such as to acrolein, in the catalytic membrane reactor (CMR) compared to the fixed bed reactor (FBR). For example, a selectivity of 54.85% for acrolein in the liquid phase was obtained in the CMR, while only 8.31% was achieved in the FBR. (C) 2003 Elsevier B.V. All rights reserved.

Selective Extraction of Mercury(II) by 1-Naphthylthiourea-Methyl Isobutyl Ketone System

Selective extraction of Mercury(II) using 1-naphthylthiourea-methyl isobutyl ketone (ANTU-MIBK) system from hydrochloric acid solutions (0.1-10 M) has been studied. Influence of foreign ions, acid and ligand concentrations has been investigated. Addition of ANTU in MIBK enhanced, extraction capacity of MIBK to several times. Low effect of foreign ions and high separation factors for a number of metal ions determined at 0.5 M hydrochloric acid concentration evaluated the proposed method efficient and selective. The experimental data obtained from application of the method for extraction of mercury from a synthetic aqueous solution reveal that more than 99% mercury can be separated from cadmium, zinc and selenium in a single step with five minutes equilibration

Synthesis and metallophilic properties of troponoid thiocrown ethers

A new class of ionophores with troponoid and thiocrown ether units was prepared. Cation-binding properties of troponoid dithiocrown ethers were characterized using UV and NMR spectroscopies. They have affinity with metal ions; in particular, they showed high affinity with Hg2+. Transport of Hg2+ through a CHCl3 liquid membrane with troponoid dithiocrown ethers was examined in a U-type cell. From an aqueous solution of HgCl2 and CuCl2, Hg2+ is transferred selectively and smoothly, while the Cu2+ remained quantitatively in the original solution. The cavity size of dithiocrown ethers is one of the requirements for effective extraction and transport of Hg2+. However, derivatives with a smaller cavity still extract and transport Hg2+. A polymer-supported troponoid dithiocrown ether was prepared to transport Hg2+ effectively and repeatedly. Comparing the troponoid dithiocrown ether with the benzenoid dithiocrown ether with a similar cavity size, the former was more effective for the transport of Hg2+. It is proposed that the tropone ring assisted the release of Hg2+ from the complex by Coulomb repulsion between the protonated tropone ring and Hg2+.

Silver nanocluster-based fluorescent sensors for sensitive detection of Cu(II)

In this work, we report the first application of water-soluble fluorescent Ag nanoclusters in fluorescent sensors. The fluorescence of poly(methacrylic acid) (PMAA)-templated Ag nanoclusters was found to be quenched effectively by Cu2+, but not when other common metal ions were present. By virtue of the specific response toward the analyte, a new, simple, and sensitive fluorescent method for detecting Cu2+ has been developed based on Ag nanoclusters.

Properties of poly(sodium 4-styrenesulfonate)-ionic liquid composite film and its application in the determination of trace metals combined with bismuth film electrode

A new kind of bismuth film modified electrode to sensitively detect trace metal ions based on incorporating highly conductive ionic liquids 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIMPF6) in solid matrices at glassy carbon (GC) was investigated. Poly(sodium 4-styrenesulfonate) (PSS), silica, and Nafion were selected as the solid matrices. The electrochemical properties of the mixed films modified GC were evaluated. The electron transfer rate of Fe(CN)(6)(4-)/Fe(CN)(6)(3-) can be effectively improved at the PSS-BMIMPF6 modified GC.

Self-assembly of guest-induced calix[4]arene nanocapsules into three-dimensional molecular architecture

In the presence of NH3-Ag+-NH3, the calix[4]arenes can be induced into dimeric nanocapsules, which can be used as building units constructing a 3D molecular architecture with the appropriate secondary ligands and metal ions.

The solid-liquid extraction of yttrium from rare earths by solvent (ionic liquid) impreganated resin coupled with complexing method

A kind of solvent (ionic liquid) impreganated resin (IL-SIR) was developed herein for ameliorating imidazolium-type IL-based liquid-liquid extraction of metal ions. In this study, [C(8)mim][PF6] containing Cyanex923 was immobilized on XAD-7 resin for solid-liquid extraction of rare earth (RE). The solid-liquid extraction contributed to ameliorating mass transfer efficiency, i.e. shortening equilibrium time from 40 min to 20 min, increasing extraction efficiency from 29% to 80%. In additional, the novel IL-SIR could separate Y(III) from Sc(III), Ho(III), Er(III), Yb(III) effectively by adding water-soluble complexing agent.

Mass transfer kinetics of neodymium(III) extraction by calix[4]arene carboxylic acid using a constant interfacial area cell with laminar flow

BACKGROUND: Thermodynamics and kinetics data are both important to explain the extraction property. In order to develop a novel separation technology superior to current extraction systems, many promising extractants have been developed including calixarene carboxylic acids. The extraction thermodynamics behavior of calix[4]arene carboxylic acids has been reported extensively. In this study, the mass transfer kinetics of neodymium(III) and the interfacial behavior of calix[4]arene carboxylic acid were investigated.

The separation of Cerium(IV) from nitric acid solutions containing Thorium(IV) and Lanthanides(III) using pure [C(8)mim]PF6 as extracting phase

The extraction behavior of Ce(IV) along with Th(IV) and Ln(III) (Ln = Ce, Gd, Yb) nitrate by pure ionic liquid, [C(8)mim]PF6, was investigated. [C(8)mim]PF6 alone showed good extraction ability for Ce(IV), while it was slight for Th(IV) and negligible for Ln(III). The extraction behavior of Ce(IV) by [C(8)mim]PF6 was particularly studied, and the most probable extraction mechanism proposed was the anion exchange mechanism. Moreover, the stripping of Ce(IV) from IL phase was also investigated. The Ce(IV) in IL phase can be quantitatively recovered by water.

Synergistic extraction of rare earths using acid-base coupling extractants of calix[4]arene carboxyl derivative and primary amine N1923

Synergistic effect in the extraction of rare earth (RE) metals by the acid-base coupling (ABC) extractants of calix[4]arene carboxyl derivative Bu-t[4]CH2COOH (H(4)A) and primary amine N1923 (RNH2) has been investigated. The extraction of RE was enhanced by the addition of sodium cations into the aqueous phase not only in the extraction system of Bu-t[4]CH2COOH alone but also in the mixture of Bu-t[4]CH2COOH and N1923. The separation factors (SFs) indicating the extraction selectivity of adjacent RE elements became higher in the mixture system.

金属离子与钙调蛋白相互作用的基质辅助激光解析电离飞行时间质谱研究

Calmodulin is a ubiquitous calcium-binding protein in eukaryote cells and engages in various important biological pathways. In the present study, binding interactions between several metal ions and calmodulin were nvestigated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS).The results revealed that the specific binding of metal ions with the protein could be detected using MALDI-TOF MS.

Synthesis of N-Methylimidazolium Functionalized Strongly Basic Anion Exchange Resins for Adsorption of Cr(VI)

N-Methylimidazolium functionalized strongly basic anion exchange resins in the Cl- form (RCI) and SO46- form (R2SO4) were synthesized and employed for adsorption of Cr(VI) from aqueous solution. FT-IR and elementary analysis proved the structures of anion exchange resins and the content of functional groups. The gel-type strongly basic anion exchange resins had high thermal stability according to TGA and good chemical stability under the experimental conditions. The adsorption behaviors of Cr(VI) on RCI and R2SO4 were studied using the batch technique. It was shown that adsorption equilibrium was reached rapidly within 60 min. The adsorption data for RCI and R2SO4 were consistent with the Langmuir isotherm equation.