Synthesis of novel palladium(0) nanocatalysts by microorganisms from heavy-metal-influenced high-alpine sites for dehalogenation of polychlorinated dioxins.
Synthesis of novel palladium(0) nanocatalysts by microorganisms from heavy-metal-influenced high-alpine sites for dehalogenation of polychlorinated dioxins.
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DOI：
10.1016/j.chemosphere.2014.07.030
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发表时间：
2014-12
期刊：
影响因子：
8.8
通讯作者：
M. Schlüter;Thomas Hentzel;Christian Suarez;Mandy Koch;W. Lorenz;L. Böhm;R. Düring;K. Koinig;M. Bunge
中科院分区：
文献类型：
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作者：
M. Schlüter;Thomas Hentzel;Christian Suarez;Mandy Koch;W. Lorenz;L. Böhm;R. Düring;K. Koinig;M. Bunge
为了寻找新的水相系统来催化具有环境和工业重要性的反应，我们使用“绿色”方法制备了新型生物生成钯（Pd）纳米催化剂，该方法基于从自然受重金属影响的高高山地区分离的微生物。细菌和真菌从蛇纹石影响的池塘（Totalp地区，Parsenn，靠近达沃斯，graub<s:1> nden，瑞士）中富集和分离。使用96孔微滴板自动检测对生长动力学的影响，允许同时培养和在线分析Pd(II)-和Ni（II）介导的生长抑制。选择耐受高达3mm Pd（II）的Totalp池塘微生物和细菌分离物，在微生物界面上培养和还原合成Pd(0)纳米催化剂。在甲酸盐作为电子给体还原Pd（II）的过程中，Pd(0)纳米粒子形成并沉积在细胞包膜中。在耐Pd（II）的alpinepseudomasspecies存在下制备的Pd(0)催化剂在模型多氯二恶英同系物的还原脱卤反应中具有催化活性。这是首次报道在微生物存在下合成的Pd(0)催化多氯二苯并对二恶英（pcdd）的还原脱氯。由于“bioPd(0)”更倾向于通过非侧氯化中间体催化脱氯反应，因此这种途径可能通过“安全途径”对pcdd进行解毒。微生物是否会形成具有催化活性的金属催化剂（如Zn、Ni、Fe），以及涉及这些催化剂的过程是否会改变高山生境中持久性有机污染物（POPs）的命运和运输，这些都有待确定。
In a search for new aqueous-phase systems for catalyzing reactions of environmental and industrial importance, we prepared novel biogenerated palladium (Pd) nanocatalysts using a “green” approach based on microorganisms isolated from high-alpine sites naturally impacted by heavy metals. Bacteria and fungi were enriched and isolated from serpentinite-influenced ponds (Totalp region, Parsenn, near Davos, Graubünden, Switzerland). Effects on growth dynamics were monitored using an automated assay in 96-well microtiter plates, which allowed for simultaneous cultivation and on-line analysis of Pd(II)- and Ni(II)-mediated growth inhibition. Microorganisms from Totalp ponds tolerated up to 3 mM Pd(II) and bacterial isolates were selected for cultivation and reductive synthesis of Pd(0) nanocatalysts at microbial interfaces. During reduction of Pd(II) with formate as the electron donor, Pd(0) nanoparticles were formed and deposited in the cell envelope. The Pd(0) catalysts produced in the presence of Pd(II)-tolerant AlpinePseudomonasspecies were catalytically active in the reductive dehalogenation of model polychlorinated dioxin congeners. This is the first report which shows that Pd(0) synthesized in the presence of microorganisms catalyzes the reductive dechlorination of polychlorinated dibenzo-p-dioxins (PCDDs). Because the “bioPd(0)” catalyzed the dechlorination reactions preferably via non-lateral chlorinated intermediates, such a pathway could potentially detoxify PCDDs via a “safe route”. It remains to be determined whether the microbial formation of catalytically active metal catalysts (e.g., Zn, Ni, Fe) occursin situand whether processes involving such catalysts can alter the fate and transport of persistent organic pollutants (POPs) in Alpine habitats.