异化金属还原菌的研究进展

微生物利用金属氧化物作呼吸作用的最终电子受体是一种新的代谢途径。该过程微生物利用有机底物异化还原金属氧化物进行生长代谢。异化金属还原菌对于研究探索古生物呼吸形式、界定生命的上限温度等生命科学问题具有重要研究价值,同时在生物整治、微生物燃料电池等方面具有广阔的应用前景。对异化金属还原菌进行了综述,并对这类菌的研究应用给了评述和展望。     

异化金属还原菌的研究进展*

微生物利用金属氧化物作呼吸作用的最终电子受体是一种新的代谢途径。该过程微生物利用有机底物异化还原金属氧化物进行生长代谢。异化金属还原菌对于研究探索古生物呼吸形式、界定生命的上限温度等生命科学问题具有重要研究价值,同时在生物整治、微生物燃料电池等方面具有广阔的应用前景。对异化金属还原菌进行了综述,并对这类菌的研究应用给予评述和展望。     

深海热液区微生物矿化过程的功能群和分子机制

深海热液区富含铁、锌、铜等含金属矿物(硫化物、氧化物、碳酸盐等)和无机小分子气体(H_2S、H_2、CO_2、CH_4等),具有独特的生态系统。微生物是深海热液生态系统的主要生产者和重要组成,并以控制矿化和诱导矿化两种途径参与了深海热液区的生物地球化学循环。在深海热液区存在着不同类型的微生物参与了生物矿化过程,如硫氧化菌、金属氧化菌、硫还原菌和金属还原菌等。本文详述了这些微生物参与的生物矿化现象、菌群多样性和矿化过程的分子机制,并对研究微生物矿化的研究工作进行了展望。     

异化Fe(Ⅲ)还原酶促反应及调控机制的研究进展

异化Fe(Ⅲ)还原菌不是分类学上的概念,它具有系统发育及环境来源多样性的特点。与其他大多数的电子受体不同,在近中性pH值条件下,Fe(Ⅲ)的溶解度很低,通常以不溶性的Fe(Ⅲ)氧化物的形式存在。目前,对微生物如何获得和还原不溶性Fe(Ⅲ)的机理仍缺乏系统的了解。以希瓦氏菌和地杆菌为例,本文综述了3种异化Fe(Ⅲ)还原的酶促反应机制及其分子调控机理：异化Fe(Ⅲ)还原菌与Fe(Ⅲ)氧化物直接接触机制、电子穿梭体的作用机制、铁载体作用机制,多种膜蛋白特别是多血红素的细胞色素蛋白参与微生物的异化Fe(Ⅲ)还原过程,并形成复杂的调控网络。此外,本文也对异化Fe(Ⅲ)还原酶促反应及其分子调控机理将来的研究方向进行了展望,以期对这一重要的生化过程有更为全面的认识。     

偶氮染料的微生物脱色研究进展

微生物法是染料废水治理的重要方法。本文综述了特异性酶作用下好氧细菌和真菌对偶氮染料的脱色以及厌氧条件下氧化还原介质作为电子穿梭体时偶氮染料的非特异性还原过程。指出厌氧偶氮还原是偶氮染料还原的主要形式, 电子供体不同脱色效率不同。对目前生物法去除偶氮染料存在的问题进行了分析, 提出了相应的对策措施。     

利用微生物重组技术促进羰基不对称还原研究进展

手性醇是许多手性药物合成的关键手性砌块,利用微生物细胞催化相应前手性羰基化合物不对称还原,是合成手性醇的重要方法之一。但应用野生微生物催化时,反应的时空产率、立体选择性较低。详细介绍了利用微生物重组技术以促进前手性羰基化合物不对称还原反应合成手性醇的国内外研究进展。从酶的种类、表达系统以及辅酶再生系统3个方面对重组细胞催化反应体系的构建进行了概述。同时按照反应底物的类型,对重组微生物在催化不同类型羰基化合物不对称还原合成手性醇中的应用分别进行了归纳和介绍。     

肠道微生物代谢苷类化合物的研究进展CSCD

肠道微生物对苷类化合物的体内代谢十分重要,可分泌代谢酶进行脱糖基、脱甲基、脱羟基、水解和氧化还原等反应将苷代谢生成次级苷、苷元或其他代谢产物,从而促进苷类药物的吸收并发挥药效。本文论述了肠道微生物及代谢酶对苷类化合物代谢的意义,总结了肠道微生物对不同结构类型的苷类化合物的代谢规律及代谢产物,为了解苷类药物的疗效基础、作用机理及利用微生物转化开发苷类药物提供参考。     

氢酶结构及催化机理研究进展

氢酶是一类催化氢的氧化或质子还原的酶,它在微生物产氢过程中扮演着重要角色。根据氢酶所含的金属元素,可分为NiFe_氢酶、Fe-氢酶和不含金属元素的metal_free氢酶。大多数氢酶含有金属原子,它们参与氢酶活性中心和[Fe_S]簇的形成。氢酶的活性中心直接催化氢的氧化与质子的还原,[Fe_S]簇则参与氢酶催化过程中电子的传输。目前已有数种NiFe_氢酶和Fe_氢酶的X射线衍射晶体结构被阐明。根据metal_free氢酶的序列特征,推断其结构与NiFe_氢酶和Fe_氢酶之间存在较大差异。对氢酶活性中心和[Fe_S]簇的深入研究,揭示了氢酶催化反应的机理。     

CO2生物转化关键酶固定体系构筑研究进展与挑战

酶催化CO₂还原制备高值化学品对缓解全球环境和能源危机具有重要意义,利用甲酸脱氢酶(formate dehydrogenase,FDH)或多酶级联还原CO₂制备甲酸/甲醇具有选择性高、条件温和的优势,但关键酶活性低、稳定性差和重复利用率低的问题限制了其规模化应用,酶的固定化为这些问题提供了有效解决方案。本文总结了近年来利用膜、无机材料、金属有机框架和共价有机框架等载体对酶进行固定化的研究进展,阐释了不同固定材料和固定方式的特点和优势;进一步总结了固定化酶与电催化或光催化耦联反应体系对CO₂还原的协同效果及应用,同时指出酶固定化技术和耦联反应体系目前存在的问题并对其发展前景进行了展望。     

微生物对硒的还原及其产物的应用研究进展——纪念硒发现200周年

硒是生命必需的微量元素,以硒代半胱氨酸(Sec,第21位氨基酸)和硒代甲硫氨酸(Se-Met)的形式加入到硒蛋白(酶)中。人畜硒摄入过量或不足均会导致很多疾病。微生物参与了Se(-Ⅱ)、Se(0)、Se(Ⅳ)和Se(Ⅵ)等各种价态间的转化。本文主要综述微生物对硒的还原及其生物学意义。微生物对硒的还原包括同化还原、异化还原以及在还原基础上进行的硒的甲基化。硒的同化还原主要是形成各种硒蛋白,满足微生物自身对硒的需求,食源性微生物对人畜补硒具有重要意义。高浓度硒酸盐和亚硒酸盐则可促使微生物进行异化还原并形成单质纳米硒颗粒。有的微生物会将还原态的Sec和Se-Met进一步转化为挥发态的甲基化硒。硒的异化还原和甲基化都是解毒机制,在硒污染环境的治理中具有重要意义。最后,阐述了单质纳米硒在医药、生物传感器和治理重金属污染等方面的应用前景,以及微生物合成CdSe荧光量子点的应用。     

Breathing metals as a way of life: geobiology in action

Many microbes have the ability to reduce transition metals, coupling this reduction to the oxidation of energy sources in a dissimilatory fashion. Because of their abundance, iron and manganese have been extensively studied, and it is well established that reduction of Mn and Fe account for significant turnover of organic carbon in many environments. In addition, many of the dissimilatory metal reducing bacteria (DMRB) also reduce other metals, including toxic metals like Cr(VI), and radioactive contaminants like U(VI), raising the expectations that these processes can be used for bioremediation. The processes involved in metal reduction remain mysterious, and often progress is slow, as nearly all iron and manganese oxides are solids, which offer particular challenges with regard to imaging and chemical measurements. In particular, the interactions that occur at the bacteria-mineral interfaces are not yet clearly elucidated. One DMRB, Shewanella oneidensis MR-1 offers the advantage that its genome has recently been sequenced, and with the availability of its genomic sequence, several aspects of its metal reducing abilities are now beginning to be seen. As these studies progress, it should be possible to separate several processes involved with metal reduction, including surface recognition, attachment, metal destabilization and reduction, and secondary mineral formation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Trace element uptake by L-cells as a function of trace elements in a synthetic growth medium

The concentration of trace elements in L-cells has been studied as a function of the trace metal content of the growth medium. Cells were cultured in synthetic media which contained varying trace amounts of the elements manganese, iron, cobalt, copper, zinc and molybdenum. The cellular concentration of the elements potassium, iron, copper and zinc were then determined. It was found that the cell accumulates trace metals at a different rate than they are made available. Deficiencies in zinc could be “induced” in the cell by increasing the concentration of iron, manganese and cobalt; cellular iron deficiencies were observed at larger medium concentrations of zinc, manganese, copper and cobalt. Trace metal uptake by the cell was seen to parallel the utilization by multicellular organisms.     

Reaction of oxygen with 6-hydroxydopamine catalyzed by Cu, Fe, Mn, and V complexes: identification of a thermodynamic window for effective metal catalysis

In the autoxidation of 6-hydroxydopamine, we investigated the reactivity of metals and metal complexes with a range of abilities to catalyse the reaction with oxygen. Comparing the catalytic effectiveness of aquo metals at pH 7.4, copper accelerated autoxidation 61-fold, iron 24-fold, manganese 7.3-fold, and vanadium 5.7-fold. Copper was thus the most effective catalyst despite being the weakest oxidant, indicating reduction of oxygen as rate limiting. EDTA, which decreases the reduction potential of Fe(III)/Fe(II), increased catalysis by iron 74% to almost that of aquo copper. Conversely, EDTA inhibited catalysis by copper, manganese, and vanadium. Desferrioxamine strongly inhibited catalysis by all of the metals. Histidine prevented catalysis by copper, accelerated catalysis by iron (43%), and had little effect on catalysis by manganese or vanadium. ADP and phytate inhibited catalysis by iron and manganese (50% or more), accelerated catalysis by vanadium (10-27%), and had no effect on catalysis by copper. The effects of the ligands largely reflected their influence on the reduction potential of the metal. Accordingly, addition of NaBr, which increases the reduction potential of Cu(II)/Cu(I), inhibited by 50%. In contrast, Na2SO4 augmented catalysis by copper 3-fold. Consistent with effects of OH- on reduction potentials and on metal coordination to 6-hydroxydopamine, an increase in pH to 8.0 decreased catalysis by copper and iron, but increased that of manganese 10-fold. In conclusion, the catalytic effectiveness of the metal-ligand complexes are largely attributable to their reduction potential, with steric accessibility playing secondary roles. The results delineate a window of catalytically effective potentials suitable for facile reduction and reoxidation by oxygen. By extension the results identify factors determining the pro- and antioxidant roles of ligands in metal mediated reduction of oxygen.     

Neuroglobin and cytoglobin as potential enzyme or substrate

The possible enzymatic activities of neuro- and cytoglobin as well as their potential function as substrates in enzymatic reactions were studied. Neuro- and cytoglobin are found to show no appreciable superoxide dismutase, catalase, and peroxidase activities. However, the internal disulfide bond (CD7-D5) of human neuroglobin can be reduced by thioredoxin reductase. Furthermore, our in vivo and in vitro studies show that Escherichia coli cells contain an enzymatic reducing system that keeps the heme iron atom of neuroglobin in the Fe(2+) form in the presence of dioxygen despite the high autoxidation rate of the molecule. This reducing system needs a low-molecular-weight compound as co-factor. In vitro tests show that both NADH and NADPH can play this role. Furthermore, the reducing system is not specific for neuroglobin but allows the reduction of the ferric forms of other globins such as cytoglobin and myoglobin. A similar reducing system is present in eukaryotic tissue protein extracts.     

The effect of physico-chemical parameters on speciation of trace metals insediments from inland and coastal waters of Ghana

The speciation of cadmium, lead, copper, zinc, manganese and iron into exchangeable, carbonate, reducible and organic bound fractions was studied in sediments from coastal and freshwater environments in Ghana. This was relevant as the species in which metals are stored within specific sediment components is important in determining their impact on the environment. For both coastal and inland sediments, a higher percentage of cadmium was associated with the more available exchangeable and carbonate fractions, while iron, zinc and manganese were mainly associated with the reducible and organic fractions. Lead and copper were found to have the greatest ability to form different species in the samples examined and were more evenly associated with all the fractions. The metals generally showed more ability to form different species in inland freshwaters than in coastal relatively saline waters. However, differences between inland and coastal waters were based more on whether the environments were oxidising or reducing than on whether they were fresh or saline. The metals may be divided into three groups of high mobility consisting of lead and copper; moderate mobility made up of cadmium, manganese and zinc; and low mobility, represented by iron.     

Heavy metals in some Chinese herbal plants

The concentrations of nine heavy metals, cadmium, cobalt, copper, iron, manganese, nickel, lead, zinc and mercury in 42 Chinese herbal medicinal plants were determined. Generally, all the samples studied had, relative to the other trace metals, higher concentrations of iron, manganese, and zinc. The concentration range of the metals determined was comparable to that in many of the East Asian vegetables and fruits. A few samples were found to contain relatively higher concentrations of the toxic metals such as cadmium, lead, and mercury. This was probably caused by contamination during air-drying and preservation.     

Role of menaquinone in the reduction of fumarate, nitrate, iron(III) and manganese(IV) by Shewanella putrefaciens MR-1

Abstract Mutants of Shewanella putrefaciens MR-1 deficient in menaquinone and methylmenaquinone, but which have wild-type levels of ubiquinone, retain the ability to use trimethylamine N -oxide as an electron acceptor, but they lose the ability to use nitrate, iron(III), and fumarate as electron acceptors. These mutants also show a reduced rate of manganese(IV) reduction. One of these mutants could be restored to essentially wild-type phenotype by supplementing the medium with 1,4-dihydroxy-2-naphthoic acid. A requirement for naphthoquinones in iron(III) reduction and a preference for naphthoquinones in manganese(IV) reduction provide further support that the metal reducing systems in MR-1 are linked to anaerobic respiration.     

Diphosphonucleotide phosphatase/phosphodiesterase (PPD1) from yellow lupin (Lupinus luteus L.) contains an iron-manganese center

Yellow lupin diphosphonucleotide phosphatase/phosphodiesterase (PPD1) represents a novel group of enzymes. Here we report that it possesses one iron atom and one manganese atom (1:1 molar ratio) per subunit. The enzyme exhibits visible absorption maximum at ∼530 nm. Prolonged oxidation of PPD1 leads to loss of the charge-transfer band and catalytic activity, whereas after reduction PPD1 remains active. Replacement of conserved amino-acid residues coordinating metals results in the loss of enzymatic activity. Despite low amino-acid sequence homology of PPD1 to well-characterized ∼55-kDa purple acid phosphatases, their overall fold, topology of active center and metal content are highly similar.     

Observations on the diagenetic behavior of arsenic in a deep coastal sediment

Vertical profiles of total dissolved arsenic, manganese and iron, pH, Eh and rates of sulfate reduction were determined in a freshly-collected box core from a 335m depth station in the Laurentian Trough. The relationships observed between the profiles were further examined in the laboratory by measuring these same parameters with time in surficial sediment slurries as the Eh decreased in response to biological activity or chemical alteration.Both field and laboratory observations have shown that arsenic is released predominantly as As(III) into reducing sediment porewaters. This occurs after the dissolution of manganese oxides and at the same time as the dissolution of iron oxyhydroxides and the onset of sulfate reduction. Laboratory experiments indicated that sulfate reduction and the production of sulfide ions are not solely responsible for the release of arsenic to the porewaters, although this process is necessary to create and maintain a highly reducing environment conducive to rapid iron dissolution.The diagenesis of arsenic in Laurentain Trough sediments involves the simultaneous release of arsenic and iron at a subsurface depth, followed by its removal from porewaters by precipitation and adsorption reactions after migration by diffusion along concentration gradients. A qualitative model is presented to describe the behavior of arsenic in coastal marine sediments.Present address: Department of Geological Sciences, McGill University, 3450 UniversityStreet, Montreal, Quebec H3A 2A7, Canada     

Deregulation of transition metals homeostasis is a key feature of cadmium toxicity in Salmonella

Cadmium is a highly toxic metal whose presence in the environment represents a challenge for all forms of life. To improve our knowledge on cadmium toxicity, we have explored Salmonella Typhimurium responses to this metal. We have found that cadmium induces the concomitant expression of the cation efflux pump ZntA and of the high affinity zinc import system ZnuABC. This observation suggests that cadmium accumulation within the cell induces a condition of apparent zinc starvation, possibly due to the ability of this metal to compete with zinc for the metal binding site of proteins. This hypothesis is supported by the finding that strains lacking ZntA or ZnuABC are hyper-susceptible to cadmium and that the cadmium-induced growth defect of a znuABC mutant strain is largely relieved by zinc supplementation. A similar growth defect was observed for a mutant with impaired ability to acquire iron, whereas cadmium does not affect growth of a strain defective in manganese import. Cadmium also influences the expression and activity of the two cytoplasmic superoxide dismutases FeSOD and MnSOD, which are required to control cadmium-mediate oxidative stress. Exposure to cadmium causes a reduction of FeSOD activity in Salmonella wild type and the complete abrogation of its expression in the strain defective in iron import. In contrast, although MnSOD intracellular levels increase in response to cadmium, we observed discrepancies between protein levels and enzymatic activity which are suggestive of incorporation of non-catalytic metals in the active site or to cadmium-mediated inhibition of manganese import. Our results indicate that cadmium interferes with the ability of cells to manage transition metals and highlight the close interconnections between the homeostatic mechanisms regulating the intracellular levels of different metals.