Resubmission novel bionanocatalysts and nanomagnets from solutions and metal bearing wastes

物质的性质在纳米尺度上发生了变化，因为晶体表面的原子与晶体内部的原子具有不同的性质。纳米晶体具有很大比例的表面原子，因此可以利用这些揭示的特性，包括增强的催化/磁性能。然而，它们在制造过程中是不稳定的，并且由于它们想要凝聚而难以制造。当这种情况发生时，它们的属性就会丢失。可以通过使用分子“摇篮”来防止团聚。这是困难和昂贵的：摇篮必须保护每个纳米粒子与邻近的纳米粒子，但允许一些区域保持暴露。细菌表面提供了很好的摇篮。金属纳米颗粒是由细菌酶作用和局部生物分子在细菌表面单独生长时形成的。例如贵金属（钯、铂、金）和铁（氧化物）。pm被细菌还原为金属状态。铁氧化物以各种矿物形式存在，这些形式是通过细菌作用和细菌影响的“反应空间”中的化学反应的组合而产生和选择的。最终的结果是支撑催化剂和磁铁，由于它们的纳米尺寸而具有特殊的性能。传统上，pm是很好的化学催化剂，而Fe-氧化物是很好的磁铁，但在纳米尺度上，这些区别变得模糊了：钯是铁磁性的，而Fe-氧化物具有催化活性。更好的是，混合的PM/Fe纳米颗粒在这两种应用中都比单一金属要好，但没有人试图生物指导合成混合纳米颗粒（称为双金属或三金属簇）。纳米粒子的不稳定性使得用化学方法做到这一点非常困难。细菌可以从混合溶液中制造混合金属纳米粒子，它们甚至可以通过从液体废物中清除金属来做到这一点。事实上，一些细菌结合的三金属化合物被发现比单纳米晶体有更好的催化性能。这可能是由于侵入的金属迫使晶体结构发生变化，从而使“埋藏”的原子认为它们更像表面的原子。类似的变化也可以通过应用电磁场（EMF；介电处理）在晶体合成期间和之后带来，但这之前没有尝试过。细菌上稳定的纳米粒子加上电介质处理的组合可以制造出新一代的超级纳米粒子，这比我们已经拥有的要先进得多。我们的目标是利用我们的细菌组合作为纳米颗粒合成和支持的催化剂，确定制造全新材料的潜力。一些细菌减少pm，一些产生氧化铁，一些两者兼而有之。我们将生物制造纳米级化学催化剂（PM），纳米磁铁（Fe），交换得到PM-磁铁和Fe-催化剂，然后将它们结合起来制造新的PM/Fe杂化体。我们将把我们制造的东西与我们制造它的方式联系起来，即细菌活性/表面特性和制造的晶体。工业合作伙伴将电介质处理生物纳米粒子，以进一步提高其性能，与卡迪夫大学的合作将使用电子显微镜，能够看到我们所做的东西，直到原子水平。我们将在大学里对生物纳米材料与商业标准材料进行催化和磁性测试。我们将主要使用纯金属溶液和菌株进行基础研究。最后，对于最好的细菌，我们将简要地看看由采矿废物（铁）和工业废物（Pd/Au）制成的新型生物异常材料的例子，因为我们知道这些材料可以更好地工作。我们将使用多功能细菌，也有一些通过适当的突变增强的细菌

The property of matter changes at the nanoscale, because atoms at the surface of a crystal have different properties from those buried within it. Nanocrystals have a large proportion of surface atoms so these revealed properties could be utilised, including enhanced catalytic/magnetic properties. However they are unstable during manufacture and are difficult to make because they want to agglomerate. When this happens their properties are lost. Agglomeration can be prevented by using molecular 'cradles'. This is difficult and expensive: the cradle must shield each nanoparticle from its neighbours, but allow some area to remain exposed. Bacterial surfaces provide good cradles. Metallic nanoparticles are made by bacterial enzyme action, and cradling by local biomolecules as they grow, individually, on bacterial surfaces. Examples are precious metals (PMs: Pd,Pt,Au) and iron (oxides). PMs are reduced by bacteria to the metallic state. Fe oxides exist in various mineral forms which are made and chosen via combinations of bacterial action, and chemical reactions in the bacterially-influenced 'reaction space'. The net results are supported catalysts & magnets with special properties attributable to their nanosize. Traditionally PMs make good chemical catalysts, and Fe-oxides make good magnets, but at the nanoscale these distinctions blur: palladium is ferromagnetic while Fe oxides have catalytic activity. Even better, hybrid PM/Fe nanoparticles are BETTER in both applications than single metals but nobody has attempted to bio-direct the synthesis of hybrid nanoparticles (called bimetallic or trimetallic clusters). The instability of nanoparticles makes this very difficult indeed using chemistry. Bacteria can make mixed metal nanoparticles from mixed solutions and they can even do this by scavenging the metals from liquid wastes. Indeed, some bacteria-bound trimetallics were found to have better catalytic properties than mono- nanocrystals. This may be due to the intruding metal forcing changes in the crystal structure so that 'buried' atoms are persuaded to think that they are more like surface ones. Similar changes could also be brought about by application of electromagnetic fields (EMF; dielectric processing) during and following crystal synthesis but this has not been tried before. A combination of stable nanoparticles on bacteria plus dielectric processing could make a new generation of supernanoparticles, far in advance of what we already have. We aim to define the potential for making completely new materials using a portfolio of our bacteria as the catalysts for nanoparticle synthesis, and support. Some bacteria reduce PMs, some make ferric oxides, some do both. We will biomanufacture nanoscale chemical catalysts (PMs), nanomagnets (Fe), swop to get PM-magnets and Fe-catalysts and then combine them to make novel PM/Fe hybrids. We will relate what we make to how we make it, i.e the bacterial activity/surface properties and the crystals made. The industrial Partner will dielectric-process the bionanoparticles to further enhance their properties and a collaboration with Cardiff will use electron microscopy to be able to see what we have made, down to the atomic level. We will do example catalytic and magnetic testing of the bionanomaterials in the Universities against commercial standard materials. Mainly we will use pure metal solutions and bacterial strains for fundamental study. Finally, with the best bacteria, we will briefly look at example novel bionanomaterials made from mining wastes (Fe) and industrial wastes (Pd/Au) since we know these can work even better. We will use multifunctional bacteria and also some enhanced by mutations as appropriate