Impact of Nanoparticle Aggregation on Protein Recovery through a Pentadentate Chelate Ligand on Magnetic Carriers

The growing need for more efficient separation techniques still dominates downstream processing of biomolecules, thus encouraging the continuous development of advanced nanomaterials. In this paper we present an improved process for recovering recombinant histidine tagged green fluorescent protein from an <i>E. coli</i> cell lysate. Superparamagnetic core–shell nanocarriers are functionalized with a pentadentate chelate affinity ligand and then loaded with metal ions (Cu²⁺, Ni²⁺, or Zn²⁺). The separation process yields high binding capacity (250 mg/g), good selectivity, purity >98%, good recyclability with 90% capacity after 9 cycles, and long-term stability. We determined the main physical properties of the magnetite-based nanoparticles such as saturation magnetization (59 A m²/kg), primary particle diameter (22 ± 4 nm), and specific surface area (89 m²/g). Our results show that this material is a promising tool for bioseparation applications. One special focus of the work includes analyzing the changes in the hydrodynamic size distribution using dynamic light scattering and transmission electron microscopy. We relate these effects to different interaction levels in the system and discuss how the stronger aggregation of the magnetite core is the main limiting factor for the separation yield, leading to a considerable decrease in the number of metal ions available for biomolecular capture. Otherwise weaker interactions lead instead to agglomeration effects that have no impact on the binding capacity of the system. The simple relation between the size of the aggregated units and the size of the primary particles corresponds approximately to the relation between the number of existing binding sites and the actual protein binding in the separation process. Compared with that, the effect of steric hindrance among proteins is of less significance

Direct Observation of Photoinduced Tautomerization in Single Molecules at a Metal Surface

Molecular switches are of fundamental importance in nature, and light is an important stimulus to selectively drive the switching process. However, the local dynamics of a conformational change in these molecules remain far from being completely understood at the single-molecule level. Here, we report the direct observation of photoinduced tautomerization in single porphycene molecules on a Cu(111) surface by using a combination of low-temperature scanning tunneling microscopy and laser excitation in the near-infrared to ultraviolet regime. It is found that the thermodynamically stable trans configuration of porphycene can be converted to the metastable cis configuration in a unidirectional fashion by photoirradiation. The wavelength dependence of the tautomerization cross section exhibits a steep increase around 2 eV and demonstrates that excitation of the Cu d-band electrons and the resulting hot carriers play a dominant role in the photochemical process. Additionally, a pronounced isotope effect in the cross section (∼100) is observed when the transferred hydrogen atoms are substituted with deuterium, indicating a significant contribution of zero-point energy in the reaction. Combined with the study of inelastic tunneling electron-induced tautomerization with the STM, we propose that tautomerization occurs via excitation of molecular vibrations after photoexcitation. Interestingly, the observed cross section of ∼10^–19 cm² in the visible–ultraviolet region is much higher than that of previously studied molecular switches on a metal surface, for example, azobenzene derivatives (10^–23–10^–22 cm²). Furthermore, we examined a local environmental impact on the photoinduced tautomerization by varying molecular density on the surface and find substantial changes in the cross section and quenching of the process due to the intermolecular interaction at high density

Threshold Energies for Single-Carbon Knockout from Polycyclic Aromatic Hydrocarbons

We have measured absolute cross sections for ultrafast (femtosecond) single-carbon knockout from polycyclic aromatic hydrocarbon (PAH) cations as functions of He–PAH center-of-mass collision energy in the 10–200 eV range. Classical molecular dynamics (MD) simulations cover this range and extend up to 10⁵ eV. The shapes of the knockout cross sections are well-described by a simple analytical expression yielding experimental and MD threshold energies of <i>E</i>_th^Exp = 32.5 ± 0.4 eV and <i>E</i>_th^MD = 41.0 ± 0.3 eV, respectively. These are the first measurements of knockout threshold energies for molecules isolated in vacuo. We further deduce semiempirical (SE) and MD displacement energies, i.e., the energy transfers to the PAH molecules at the threshold energies for knockout, of <i>T</i>_disp^SE = 23.3 ± 0.3 eV and <i>T</i>_disp^MD = 27.0 ± 0.3 eV. The semiempirical results compare favorably with measured displacement energies for graphene (<i>T</i>_disp = 23.6 eV)

Halide-Free Synthesis and Tribological Performance of Oil-Miscible Ammonium and Phosphonium-Based Ionic Liquids

Due to their low vapor pressures, nonflammability, high thermal stabilities, and excellent tribological properties ionic liquids (ILs) are highly attractive lubricant base oils and additives. However, for practical applications of ILs in lubrication, two requirements are often limiting, the required miscibility with standard mineral oils (≥5 wt %) and the complete absence of corrosive halide ions in the ionic liquid. Moreover, the need for full compatibility with standard oil additives reduces the number of potential IL-based lubricant additives even further. In this contribution, an economic halide-free synthesis route to oil-miscible ionic liquids is presented, and very promising tribological properties of such ILs as base oil or additive are demonstrated. Therefore, sliding tests on bearing steel and XPS analysis of the formed surface films are shown. Corrosion test results of different bearing metals in contact with our halide-free ILs and (salt) water prove their applicability as real life lubricants. In the sustainable chemistry and engineering context, we present a halide-free design approach for ionic performance chemicals that may contribute to significant energy savings due to their enhanced lubrication properties