Study on the Characterization and Kinetics of Immobilized Lipase

1 Rusults Most enzymes, including lipase, play a key role in biotechnology, but their usage is quite limited because of poor recovery, yield, limited re-usability and rapid inactivation in the soluble state. Immobilization enzymes offer advantages over free enzymes because of the availability of a choice of batch or continuous processes, rapid termination of reactions, controlled product formation, ease of enzyme removal from the reaction mixture, and adaptability to various engineering designs.In this study, lipase from Candida Antarctica was immobilized on magnetic composite microsphere by physical adsorption. Different factors which affect enzymatic activities was investigated by measuring the hydrolysis of olive oil, and comparative studies of pH,temperature, thermal stability and apparent Km between free lipase and immobilized lipase were conducted. The value of apparent Km of immobilized lipase was lower than that of the free lipase. The optimum pH and temperature of the immobilized lipase were 8.0 and 50 ℃. Meanwhile,We found the immobilized lipase exhibited remarkable stability in medium alkalinity, good reusability and better thermal stability.     

Fine grain tungsten produced with nanoscale powder

Nanoscale tungsten powder was prepared by reducing nanoscale tungsten trioxide in hydrogen to WO_2.90 and further to W powder. After compacted with a rubber die, the nanoscale tungsten powder was sintered in a high-temperature dilatometer to investigate its shrinkage process. The results show that the compact of the nanoscale tungsten powder starts to shrink at 1050℃ and ends at 1500℃. The shrinkage rate reaches the maximum value at 1210℃. The relative density of sintered samples is 96.4%, and its grain size is about 5.8 μm.     

He-Ar isotopic system of fluid inclusions in pyrite from the molybdenum deposits in south margin of North China Block and its trace to metallogenetic and geodynamic background

The helium and argon isotopic compositions of the ore-forming fluids from the molybdenum deposits such as Jinduicheng, Donggou, Shijiawan, and Sandaozhuang, which are located in the East Qinling molybdenum belt in south margin of North China Block （SMCNB）, are reported in this paper. The origin and the evolution of the ore-forming fluids and their coupled-relationships with the intra-continental collision and orogenic process of Qinling Orogen in Mesozoic-Cenozoic have been discussed. The 3He/4He and 40Ar/36Ar values （3He/4He=1.38-3.64 Ra, and 40Ar/36Ar=295.68-346.39, respectively） of the fluid inclusions in pyrite from the molybdenum deposits in East Qinling suggest that, the ore-forming fluid system is mixed by two end members. One is the high temperature deep-derived fluid congenetic with the porphyries generated by crust-mantle mixing, and the other is the low-temperature meteoric water which is rich in crustal radiogenic He with the component of atmospheric Ar. From the Pb isotopic composition, and ore-bearing potential of the porphyry and the regional stratum, we can conclude that the ore-forming materials of the deposits in the East Qinling molybdenum belt are derived from the deep source by the mixing of lower crust and upper mantle. Therefore, the formation of the molybdenum deposits in SMNCB can be related to the crust-mantle interaction, which is accompanied by the intra-continental orogenic and extension process in the post-collision period of Qinling Orogen. The granitic porphyries which are related to Mo mineralization are not simple crust-remelting type granites or S type granites, but belong to syntexis-type or mantle-derived granites, hence their formation has a profound and regional geodynamic background.     

New Catalysts for ROMP

Ring Opening Metathesis Polymerization （ROMP） is based on the olefin metathesis reaction, which requires transition metal catalysts. Mainly molybdenum, tungsten and ruthenium based catalysts have up to now been used. The “in-between” metal rhenium was only rarely applied in olefin metathesis reactions, and not at all in ROMP processes. We have found that cationic phosphine substituted dinitrosyl rhenium complexes 1a and 1b effectively catalyze ROMP of norbonene, dicyclopentadiene and of cyclooctene. See Fig. 1.     

Mycotoxin fumonisins: Health impacts and biosynthetic mechanism

Fumonisins are one of the most important groups of mycotoxins in agriculture and the food industry. They are produced by several widespread fungal pathogens of corn. Fumonisin contamination in maize?derived food and feeds causes several fatal diseases in livestock and poses a significant cancer risk to humans (Group 2B carcinogen). In the recent years, fumonisins have become a hot area in mycotoxin research. This review attempts to highlight the progress in the studies of molecular mechanisms for fumonisin biosynthesis and mode of action. The current understandings in the molecular basis for the cellular effects induced by fumonisins are discussed. Special attentions are paid to introduce the progress in the characterization of individual genes and enzymes involved in the biosynthesis of fumonisins.     

Induction of phenylalanine ammonia-lyase and lipoxygenase in cotton seedlings by mechanical wounding and aphid infestation

It has been suggested that infestation of plants causes increases in the activities of phenylalanine ammonia-lyase (PAL) and lipoxygenase (LOX), key enzymes in the phenolic compounds synthesis pathway and the octadecanoid pathway, respectively. The purpose of this work is to investigate whether the infestation of cotton aphid （Aphis gossypii） and mechanical wound can cause the induction of PAL and LOX activities in cotton seedlings, and whether the induction occurs in healthy seedlings growing nearby the attacked ones. The specific activities of PAL and LOX were measured using spectrophotometric method after aphid infestation and mechanical wounding. Result indicated that PAL activity and LOX activity were greatly induced by mechanical wounding and aphid infestation in cotton seedlings. The induction of PAL and LOX occurred not only in wounded and infested seedlings but also in intact healthy seedlings growing nearby. After exposed to the aphid infestation-induced volatiles, the specific activity of PAL in cotton seedlings increased by 6% at 24 h, 80% at 48 h, 235% at 72 h compared to the control, and the specific activity of LOX increased by 18% at 24 h, 34% at 48 h, 24% at 72 h, respectively. In comparison, the specific activity of PAL in unwounded seedlings exposed to wound-induced volatiles increased by 0.0 at 24 h, 200% at 48 h, 164% at 72 h, respectively and the specific activity of LOX increased by 28% at 24 h, 37% at 48 h, 8% at 72 h, respectively. It suggests that the induced volatiles are involved in plant-plant communication as airborne transferred signals.     

Phosphodiesterase 4 and compartmentalization of cyclic AMP signaling

Cyclic AMP (cAMP), as a second messenger, plays a critical role in cellular signaling transduction. However, it is not clear how this apparently identical cAMP signal induces divergent physiological re- sponses. The potential explanation that cAMP signaling is compartmentalized was proposed by Buxton and Brunton twenty years ago. Compartmentalization of cAMP signaling allows spatially distinct pools of protein kinase A (PKA) to be differently activated. Research on cAMP signaling has regained impetus in many fields of life sciences due to the progress in understanding cAMP signaling complexity and functional diversity. The cAMP/PKA signaling compartments are maintained by A-kinase anchoring proteins (AKAPs) which bind PKA and other signaling proteins, and by PDEs which hydrolyse cAMP and thus terminate PKA activity. PDE4 enzymes belong to PDE superfamily and stand at a crossroad that allows them to integrate various signaling pathways with that of cAMP in spatially distinct com- partments. In the current review, the nomenclature, taxonomy and gene expression of PDE4, and the system and region of its effect are described. In addition, the idiographic molecules, mechanisms, and regulation models of PDE4 are summarized. Furthermore, the important roles PDE4 plays in the matu- ration of rat granulosa cells and cAMP signaling compartmentalization are discussed.     

Origin of ore-forming fluid in the Piaotang tungsten deposit in Jiangxi Province: Evidence from helium and argon isotopes

The Piaotang tungsten deposit in Jiangxi Province is one of the most important tungsten deposits in the South China Tungsten Metallogenic Province.In this study,we selected wolframite and chalcopyrite from the main mineralizing stage of the Piaotang tungsten deposit,and analyzed the helium and argon isotopic compositions in fluid inclusions of these minerals.The results show a 3He/4He ratio of 0.17 to 0.86 R/Ra,which fall within the range between continental crust(0.01―0.05 R/Ra) and air-saturated water(1 R...     

Recent Advances in Protein Extraction and Chiral Separation of Blomolecules

Reverse micelles create unique environment in organic media. They are capable of solubilizing hydrophilic biomolecules （e.g., proteins, peptides, amino acids, and DNAs） in their aqueous interior. This feature brings about the practical use of biomaterials in organic media because reverse micelles solubilize them with the intrinsic activity. In this paper, we focus on recent two topics concerning protein extraction and chiral separation of biomolecules using liquid membranes. In the first topic, we present recent attempts to extract proteins from an aqueous solution into isooctane using reverse micelles, and some important operational parameters to achieve an efficient protein transfer are discussed. Furthermore, novel function of reverse micelles as a protein activation medium is introduced. In the reverse micellar phase, denatured proteins were completely reactivated in the reverse micellar solution. The reverse micellar technique is found to be a useful tool not only for protein separation but also for protein refolding. Furthermore, we found that a cyclic ligand carixarene has an extraction ability to set up optimum conditions for protein transfer. In the second topic, we have found that a supported liquid membrane （SLM） encapsulating enzymes shows high enantioselectivity （enantioselective excess value is over 96%） in the transport of racemic pharmaceutical compound ibuprofen. A different experiment also suggests that the α-chymotrypsin-catalyzed reactions droved the enantioselective transport of L-phenylalanine based on the enantioselectivity of the enzyme. The SLM encapsulating the surfactant-enzyme complex enabled the highly enantioselective separation of racemic mixtures. It can be envisioned that arrangement of appropriate enzymes in the SLM system will allow enantioselective separation of various useful organic compounds.     

CuCrW(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) nanocomposite: mechanical alloying,microstructure, and tribological properties

The effect of alumina nanoparticle addition on the microstructure and tribological properties of a CuCrW alloy was investigated in this work. Mechanical alloying was carried out in a satellite ball mill. The tribological properties of the samples were evaluated using pin-on-disk wear tests with different pins (alumina, tungsten carbide, and steel pins). The results indicated that the tungsten carbide pin had a lower coefficient of friction than the alumina and steel pins because of its high hardness and low surface roughness. In addition, when the sliding rate was decreased, the weight-loss rate increased. The existence of alumina nanoparticles in the nanocomposite led to a lower weight-loss rate and to a change in the wear mechanism from adhesive to abrasive.     

Li1+xAlxTi2-x(PO4)3(x=0~0.4)溶胶-凝胶法合成及其性质

以乙酸锂、硝酸铝、钛酸丁酯、磷酸二氢铵为原料,利用溶胶-凝胶法合成锂离子Li_1+xAl_xTi_2-x(PO₄)₃(x=0~0.4)固体电解质体系,检测结果表明：Li_1+xAl_xTi_2-x(PO₄)₃体系具有较好的结晶性,合成的粉末与烧结片之间的结晶性与结构差异不大;当Al³⁺掺杂量逐步增加时,离子电导率逐渐增大,并在x=0.3时达到最大值,但掺杂量进一步增加时,离子电导率迅速下降;活化能的变化趋势与离子电导率相反.     

Silicon-phthalocyanine bonding with SiO2 matrix and its strong optical limiting effects

Silicon-phthalocyanine (SiPc) is chemically bonded to 3-aminopropitriethoxysilane (NH₂(CH₂)₃Si(OC₂H₅)₃, KH550) by the nucleophilic substituted reaction between the active chlorine of silicon dichlorine phthalocyanine (SiPcCl₂) and amino-group of KH550. The reacted product is hybridized with 3-glycidoxypropitrimethoxysilane (CH₂OCHCH₂O(CH₂)₃Si(OCH₃)₃, KH560) with sol-gel processing to form sol-gel inorganic material with good physical-chemical and optical properties. Due to tethering SiPc to the network, the aggregation of SiPc is effectively prevented in sol-gel derived matrix, and the doping concentration of SiPc in the form of monomer in the matrix is greatly enhanced. The cross-linkage of SiPcCl₂ and KH550 is estimated and confirmed with FT-IR spectra. The optical limiting effects (OLE) of the gel with different content of SiPc are investigated with a frequency double Q-switched Nd₃₊:YAG laser of 8 nsec. pulse.     

Magnetic properties of heteropolyoxometalates

The progress of the study on the magnetic properties of heteropolyoxometalates during the late decade is reviewed. Some anions of heteropolyoxometalates containing magnetic atoms, such as [M4(H2O)4(PW9O34)2]10- and[M4(H2O)4(P2W15O56)2]16-[M = Co(Ⅱ), Zn( Ⅱ ), Cu( Ⅱ ), Mn(Ⅱ ), Ni(Ⅱ)], and [GaW9O37M3(H2O)3]n-[M = Fe(Ⅲ), Cu(Ⅱ), Co(Ⅱ)] showed ferromagnetic and antiferromagnetic properties. The combination of heteropoly anions and organic π-donor of TTF+ (te-trathiofulvalene cation) results in a variety of magnetic properties. Furthermore, there is an interaction between the inorganic and organic components. The electrocrystallization technique can prepare the organic-inorganic salts of this kind, which will become the new member of molecular magnetic materials. Heteropoly blue is a kind of the mixed-valence complexes and its reduction electrons can be delocalized over anionic framework. The further study on the magnetic properties of heteropolyoxometalates will provide important information for the design of molecular materials.     

Syntheses and lyotropic liquid crystal properties of a series of sandwich-type tungstoarsenates heteropoly compounds with As/W ratio of 4/30

A series of sandwich-type tungstoarsenates heteropoly compounds with As/W ratio of 4/30, Na16[As4W30M4(H2O)2O112]·XH2O (M = Zn,Cu,Co,Ni,Mn and Cd), have been synthesized for the first time and structurally characterized by elemental analysis, IR and 183W NMR spectra. The crystal structure of Na16[As4W30Cu4(H2O)2O112]·63H2O was determined to be a triclinic system, of P1 symmetry, a = 1.2721(3) nm, b = 2.451 6(5) nm, c = 2.6450(5) nm, α= 89.90(3)°,β= 77.32(3)°, γ= 89.96(3)°, 2=2. Using tetrahepty lammonium bromide as a phase transfer reagent, [As4W30Cu4(H2O)2O112]16- was transferred from aqueous solution to organic phase (benzene), and the heteropolyanion lost the coordination water molecules to form the coordination-unsaturated ion. After lactic acid was added to the benzene solution, the coordination-saturation was recovered. By esterification reaction between lactic acid and cholesterin, the latter was attached to the heteropolyanion indirectly. Therefore, a new type of lyotropic liquid crystal was obtained, which was characterized by a polarimicroscope, DSC and variable temperature wide-angle X-ray diffraction.     

The first observation of Mo5+ in the passivation layer of Mo2N

Molybdenum nitride powder with S_g of 115 m² · g¹ (passivated) has been prepared by a temperature programmed reaction of MoO₃in H₂/N₂ mixture. It exhibited high catalytic activity in CO oxidation at low temperature. XPS, EPR and LRS studies have shown the existence of mixed valence states of Mo ions, especially Mo⁵⁺ ion (g(tT=1.932,g||=1.892) observed for the first time, in the passivation layer of molybdenum nitride. A surface Superoxide species, O₂ (g = 2.001, Raman band 1 124 cm¹), was found to be produced accompanying the transformation of Mo⁵⁺/Mo⁴⁺ redox pair. Evidence has been given to suggest that this surface superoxide might be responsible for CO oxidation over Mo₂N catalyst.     

无机-有机杂化材料Mo8O26(H2bpp)2的合成与表征

以无水乙醇和冰乙酸为溶剂,Co(NO₃)₂·6H₂O,（1,3 二(4-吡啶基)丙烷（bpp）和(NH₄)₆［Mo₇O₂₄］·4H₂O为反应物,在150℃下进行溶剂热反应,合成了新的无机-有机杂化材料Mo₈O₂₆(H₂bpp)₂。采用单晶X-射线衍射法测定晶体结构,通过紫外-可见-近红外反射光谱表征了晶体性能。研究表明,合成产物属单斜晶系,空间群P2₁/c,晶胞参数a=10.938(2),b=9.7351(19),c=19.649(4),β=101.74(3)° ,V=2048.5(7)A° ³;晶体结构由无机的［Mo₈O₂₆］^4-_n链和有机的(H₂bpp)²⁺离子靠静电力和氢键堆积而成;此无机-有机杂化材料对紫外光具有较强的吸收,且有一定的质子导电能力。     

Investigation on the coordinate structures of the rare earth metal complexes with edta and cydta ligands

0　IntroductionThegreatattentionhasbeenpaidtorareearthorradioactiverareearthmetalcomplexesfortheirvariousbiologicactivi ties[1 3] .Forexamples,theradioactiverareearthmetal1 53SmⅢ com plexeswerewidelyusedfortumourtherapyofbrain ,liver,lung ,heartandbonetissues[4 5] ;forrareearthmetalEuⅢandTbⅢemitinguniquefluorescence ,theircompoundswereappliedfordiagnosesofvariousdiseases[6 ,7] ;forrareearthmetalGdⅢcontainingthemosthigh spinsingleelectrons,itscomplexeswereusuallyusedforcontrastagentsofmag…     

Synthesis and crystal structure of hydroquinone-β-cyclodextrin complex

The title inclusion complex with the formula [(C₄₂H₇₀O₃₅)₂·(C₆O₂H₆)₃·(H₂O)_21.2(CH₃OH)₂] has been crystallized and characterized by single crystal X-ray analysis. The complex crystallizes in the triclinic system, space group P1, with a = 1.5500 (1), b = 1.5536(1), c = 1.8246(1) nm, α = 113.17(2), β = 99.12(2), γ = 103.37(3)o, V = 3.7739 (4) nm³, Z = 1; D_c = 1.343 g/cm³, μ = 0.124 mm^-1, F(000) = 1594, R = 0.0795 and S = 0.9639. Two independent molecules of β -cyclodextrin (β -CD) form a “head-to-head” dimer. The fairly important factor of the position and stability of the guest in the host cavity is the solvation of the polar group of the guest.     

Electrical conductivity optimization of the Na3AlF6-Al2O3-Sm2O3 molten salts system for Al-Sm intermediate binary alloy production

Metal Sm has been widely used in making Al-Sm magnet alloy materials. Conventional distillation technology to produce Sm has the disadvantages of low productivity, high costs, and pollution generation. The objective of this study was to develop a molten salt electrolyte system to produce Al-Sm alloy directly, with focus on the electrical conductivity and optimal operating conditions to minimize the energy consumption. The continuously varying cell constant (CVCC) technique was used to measure the conductivity for the Na₃AlF₆-AlF₃-LiF-MgF₂-Al₂O₃-Sm₂O₃ electrolysis medium in the temperature range from 905 to 1055℃. The temperature (t) and the addition of Al₂O₃ (W(Al₂O₃)), Sm₂O₃ (W(Sm₂O₃)), and a combination of Al₂O₃ and Sm₂O₃ into the basic fluoride system were examined with respect to their effects on the conductivity (κ) and activation energy. The experimental results showed that the molten electrolyte conductivity increases with increasing temperature (t) and decreases with the addition of Al₂O₃ or Sm₂O₃ or both. We concluded that the optimal operation conditions for Al-Sm intermediate alloy production in the Na₃AlF₆-AlF₃-LiF-MgF₂-Al₂O₃-Sm₂O₃ system are W(Al₂O₃) + W(Sm₂O₃)=3wt%, W(Al₂O₃):W(Sm₂O₃)=7:3, and a temperature of 965 to 995℃, which results in satisfactory conductivity, low fluoride evaporation losses, and low energy consumption.     

Synthesis, crystal structure and properties of binuclear manganese complex [(bipy)2Mn2(μ-O)(μ-Ac)2(H2O)2](ClO4)2

Binuclear manganese complex [(bipy)₂Mn₂(μ-O)(μ-Ac)₂(H₂O)₂](ClO₄)₂ was synthesized by the reaction of MnAc₃ · 2H₂O with 2,2′-bipyridine in the HAc-NaAc buffer (pH = 4.0). X-ray diffraction result for the single crystal shows that the crystal is monoclinic, space group C₂/C, with a = 3.408 2(7),b = 0.864 4(2),c = 2.174 9(4) nm, β= 105.2∘, V=6.186(2) nm³, Z= 8. There are two very strong peaks of UV-Vis spectrum in the range of 400–600 nm, which are similar to those of Mn catalase and Mn ribonuleotide reductase extracted from organisms. Cyclic voltammogram shows that the complex in CH₃CN undergoes quasi-reversible one-electron reduction and oxidation at E_1/2=1.15V.