Western diet increases brain metabolism and adaptive immune responses in a mouse model of amyloidosis.

Diet-induced increase in body weight is a growing health concern worldwide. Often accompanied by a low-grade metabolic inflammation that changes systemic functions, diet-induced alterations may contribute to neurodegenerative disorder progression as well. This study aims to non-invasively investigate diet-induced metabolic and inflammatory effects in the brain of an APPPS1 mouse model of Alzheimer's disease. [18F]FDG, [18F]FTHA, and [18F]GE-180 were used for in vivo PET imaging in wild-type and APPPS1 mice. Ex vivo flow cytometry and histology in brains complemented the in vivo findings. 1H- magnetic resonance spectroscopy in the liver, plasma metabolomics and flow cytometry of the white adipose tissue were used to confirm metaflammatory condition in the periphery. We found disrupted glucose and fatty acid metabolism after Western diet consumption, with only small regional changes in glial-dependent neuroinflammation in the brains of APPPS1 mice. Further ex vivo investigations revealed cytotoxic T cell involvement in the brains of Western diet-fed mice and a disrupted plasma metabolome. 1H-magentic resonance spectroscopy and immunological results revealed diet-dependent inflammatory-like misbalance in livers and fatty tissue. Our multimodal imaging study highlights the role of the brain-liver-fat axis and the adaptive immune system in the disruption of brain homeostasis in amyloid models of Alzheimer's disease.

Exploring the interfacial behavior of ruthenium complexes in ionic liquids: implications for supported ionic liquid phase catalysts.

The interaction of metal complexes with ionic liquids, with a particular focus on the stability and surface concentration of the metal centers, is crucial in applications involving catalysts based on supported ionic liquids. In this study, we synthesized the complexes [Ru(tpy)(bpy)Cl][PF6] and [Ru(tpy)(dcb)Cl][PF6] (tpy = 2,2',2''-terpyridine, bpy = 2,2'-bipyridine, dcb = 4,4'-dicarboxy-2,2'-bipyridine) and we prepared solutions using the ionic liquids (ILs) 1-ethyl-3-methylimidazolium acetate [C2C1Im][OAc] and 1-butyl-3-methylimidazolium hexafluorophosphate [C4C1Im][PF6]. The chemical environment of the Ru(II) metal center and the interfacial behavior of the complexes in the different IL solutions were determined using angle-resolved X-ray photoelectron spectroscopy (ARXPS). In [C4C1Im][PF6], [Ru(tpy)(bpy)Cl][PF6] maintains its chemical structure, while in [C2C1Im][OAc], partial changes in the chemical environment of the Ru center are indicated by XPS, likely due to ligand exchange. The presence of carboxylic acid functional groups in the bipyridyl ligand seems to inhibit this ligand exchange. The investigated complexes do not exhibit surface activity but are depleted from the IL/gas interface. These findings hold significance for the design of new supported ionic liquid phase catalysts based on Ru complexes.

The Buoy Effect: Surface Enrichment of a Pt Complex in IL Solution by Ligand Design.

Invited for the cover of this issue are the groups of Hans-Peter Steinrück and Peter Wasserscheid at the Friedrich-Alexander-Universität Erlangen-Nürnberg. The image depicts two Pt catalysts dissolved in an ionic liquid. For one of them, fluorinated side chains in the ligand system act as buoys leading to pronounced enrichment of the complex at the gas/IL interface, as is evidenced by strongly enhanced Pt signals in angle-resolved photoelectron spectroscopy. For the complex without fluorinated side chains, no such effect is observed. Read the full text of the article at 10.1002/chem.202203325.

The Buoy Effect: Surface Enrichment of a Pt Complex in IL Solution by Ligand Design.

The targeted enrichment of a Pt complex with an ionic liquid (IL)-derived ligand system in IL solution is demonstrated by using angle-resolved X-ray photoelectron spectroscopy. When the ligand system is complemented with fluorinated side chains, the complex accumulates strongly at the IL/gas interface, while in an equivalent solution of a complex without these substituents no such effect could be observed. This buoy-like behavior induces strong population of the complex at the outermost molecular layer close to surface saturation, which was studied over a range from 5 to 30 %mol . The surface enrichment was found to be most efficient at the lowest concentration, which is particularly favorable for catalytic applications such as supported ionic-liquid-phase (SILP) catalysis.

Understanding the Buoy Effect of Surface-Enriched Pt Complexes in Ionic Liquids: A Combined ARXPS and Pendant Drop Study.

Recently, we demonstrated that Pt catalyst complexes dissolved in the ionic liquid (IL) [C4 C1 Im][PF6 ] can be deliberately enriched at the IL surface by introducing perfluorinated substituents, which act like buoys dragging the metal complex towards the surface. Herein, we extend our previous angle-resolved X-ray photoelectron spectroscopy (ARXPS) studies at complex concentrations between 30 and 5 %mol down to 1 %mol and present complementary surface tension pendant drop (PD) measurements under ultraclean vacuum conditions. This combination allows for connecting the microscopic information on the IL/gas interface derived from ARXPS with the macroscopic property surface tension. The surface enrichment of the Pt complexes is found to be most pronounced at 1 %mol . It also displays a strong temperature dependence, which was not observed for 5 %mol and above, where the surface is already saturated with the complex. The surface enrichment deduced from ARXPS is also reflected by the pronounced decrease in surface tension with increasing concentration of the catalyst. We furthermore observe by ARXPS and PD a much stronger surface affinity of the buoy-complex as compared to the free ligands in solution. Our results are highly interesting for an optimum design of IL-based catalyst systems with large contact areas to the surrounding reactant/product phase, such as in supported IL phase (SILP) catalysis.

Formation and Surface Behavior of Pt and Pd Complexes with Ligand Systems Derived from Nitrile-functionalized Ionic Liquids Studied by XPS.

The front cover artwork is provided by the groups of Prof. Hans-Peter Steinrück and Prof. Peter Wasserscheid at the Friedrich-Alexander-Universität (FAU) Erlangen-Nürnberg. The image shows substitution of volatile acetonitrile ligands by a nitrile-functionalized imidazolium cation. The formed cationic complex and the counter ions exhibit a specific preferential orientation at the ionic liquid/gas interface, which can be studied by angle-resolved XPS. Read the full text of the Research Article at 10.1002/cphc.202200391.

Formation and Surface Behavior of Pt and Pd Complexes with Ligand Systems Derived from Nitrile-functionalized Ionic Liquids Studied by XPS.

We studied the formation and surface behavior of Pt(II) and Pd(II) complexes with ligand systems derived from two nitrile-functionalized ionic liquids (ILs) in solution using angle-resolved X-ray photoelectron spectroscopy (ARXPS). These ligand systems enabled a high solubility of the metal complexes in IL solution. The complexes were prepared by simple ligand substitution under vacuum conditions in defined excess of the coordinating ILs, [C3 CNC1 Im][Tf2 N] and [C1 CNC1 Pip][Tf2 N], to immediately yield solutions of the final products. The ILs differ in the cationic head group and the chain length of the functionalized substituent. Our XPS measurements on the neat ILs gave insights in the electronic properties of the coordinating substituents revealing differences in donation capability and stability of the complexes. Investigations on the composition of the outermost surface layers using ARXPS revealed no surface affinity of the nitrile-functionalized chains in the neat ILs. Solutions of the formed complexes in the nitrile ILs showed homogeneous distribution of the solute at the surface with the heterocyclic moieties preferentially orientated towards the vacuum, while the metal centers are rather located further away from the IL/vacuum interface.

Adsorption and thermal evolution of [C1C1Im][Tf2N] on Pt(111).

In the context of ionic liquid (IL)-assisted catalysis, we have investigated the adsorption and thermal evolution of the IL 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([C1C1Im][Tf2N]) on Pt(111) between 100 and 800 K by angle-resolved X-ray photoelectron spectroscopy and scanning tunneling microscopy. Defined amounts of IL in the coverage range of a complete first wetting layer were deposited at low temperature (100-200 K), and subsequently heated to 300 K, or directly at 300 K. At 100 K, the IL adsorbs as an intact disordered layer. Upon heating to 200 K, the IL stays intact, but forms an ordered and well-oriented structure. Upon heating to 250 K, the surface order increases, but at the same time STM and XPS indicate the onset of decomposition. Upon heating to 300 K, decomposition progresses, such that 50-60% of the IL is decomposed. The anion-related reaction products desorb instantaneously, and the cation-related products remain on the surface. Thereby, the surface is partly passivated, enabling the remaining IL to still be adsorbed intact at 300 K. For IL deposition directly at 300 K, a fraction of the IL instantaneously decomposes, with the anion-related products desorbing, opening free space for further deposition of IL. Hence, cation-related species accumulate at the expense of anions, until one fully closed wetting layer is formed. As a consequence, a higher dose is required to reach this coverage at 300 K, compared to 100-200 K.

On-Surface Metathesis of an Ionic Liquid on Ag(111).

We investigated the adsorption, surface enrichment, ion exchange, and on-surface metathesis of ultrathin mixed IL films on Ag(111). We stepwise deposited 0.5 ML of the protic IL diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]) and 1.0 ML of the aprotic IL 1-methyl-3-octylimidazolium hexafluorophosphate ([C8 C1 Im][PF6 ]) at around 90 K. Thereafter, the resulting layered frozen film was heated to 550 K, and the thermally induced phenomena were monitored in situ by angle-resolved X-ray photoelectron spectroscopy. Between 135 and 200 K, [TfO]- anions at the Ag(111) surface are exchanged by [PF6 ]- anions and enriched together with [C8 C1 Im]+ cations at the IL/vacuum interface. Upon further heating, [dema][PF6 ] and [OMIm][PF6 ] desorb selectively at ∼235 and ∼380 K, respectively. Hereby, a wetting layer of pure [C8 C1 Im][TfO] is formed by on-surface metathesis at the IL/metal interface, which completely desorbs at ∼480 K. For comparison, ion enrichment at the vacuum/IL interface was also studied in macroscopic IL mixtures, where no influence of the solid support is expected.

Probing Surface and Interfacial Tension of Ionic Liquids in Vacuum with the Pendant Drop and Sessile Drop Method.

We report on the surface and interface tension measurements of the two ionic liquids (ILs) [C8C1Im][PF6] and [m(PEGn)2Im]I (n = 2, 4, 6) in a surface science approach. The measurements were performed in a newly developed and unique experimental setup, which allows for surface tension (ST) measurements using the pendant drop method and for contact angle measurements using the sessile drop method under the well-defined conditions of a high vacuum (from 10-7 mbar). The setup also allows for in vacuum transfer to an ultrahigh vacuum system for surface preparation and analysis, such as in angle-resolved X-ray photoelectron spectroscopy. For [C8C1Im][PF6], we observe a linear decrease in the surface tension with increasing temperature. The ST measured under high vacuum is consistently found to be larger than under ambient conditions, which is attributed to the influence of water uptake in air by the IL. For [m(PEGn)2Im]I (n = 2, 4, 6), we observe a decrease in the ST with increasing polyethylene glycol chain length in a vacuum, similar to very recent observations under 1 bar Argon. This decrease is attributed to an increasing enrichment of the PEG chains at the surface. The ST data obtained under these ultraclean conditions are essential for a fundamental understanding of the relevant parameters determining ST on the microscopic level and can serve as a benchmark for theoretical calculations, such as molecular dynamic simulations. In addition to the ST measurements, proof-of-principle data are presented for sessile drop measurements in HV, and a detailed description and characterization of the new setup is provided.

Direct Correlation of Surface Tension and Surface Composition of Ionic Liquid Mixtures-A Combined Vacuum Pendant Drop and Angle-Resolved X-ray Photoelectron Spectroscopy Study.

We investigated the surface tension and surface composition of various mixtures of the two ionic liquids (ILs) 1-methyl-3-octyl-imidazolium hexafluorophosphate [C8C1Im][PF6] and 1,3-bis(polyethylene glycol)imidazolium iodide [(mPEG2)2Im]I in the temperature range from 230 to 370 K under ultraclean vacuum conditions. The surface tension was measured using a newly developed apparatus, and the surface composition was determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). In the pure ILs, the alkyl chains of [C8C1Im][PF6] and the PEG chains of [(mPEG2)2Im]I are enriched at the IL/vacuum interface. In the mixtures, a strong selective surface enrichment of the alkyl chains occurs, which is most pronounced at low [C8C1Im][PF6] contents. For the surface tension, strong deviations from an ideal mixing behaviour take place. By applying a simple approach based on the surface composition of the mixtures as deduced from ARXPS, we are able to predict and reproduce the experimentally measured temperature-dependent surface tension values with astonishingly high accuracy.

n-Butane, iso-Butane and 1-Butene Adsorption on Imidazolium-Based Ionic Liquids Studied with Molecular Beam Techniques.

The interaction of molecules, especially hydrocarbons, at the gas/ionic liquid (IL) surface plays a crucial role in supported IL catalysis. The dynamics of this process is investigated by measuring the trapping probabilities of n-butane, iso-butane and 1-butene on a set of frozen 1-alkyl-3-methylimidazolium-based ILs [Cn C1 Im]X, where n=4, 8 and X- =Cl- , Br- , [PF6 ]- and [Tf2 N]- . The decrease of the initial trapping probability with increasing surface temperature is used to determine the desorption energy of the hydrocarbons at the IL surfaces. It increases with increasing alkyl chain length n and decreasing anion size for the ILs studied. We attribute these effects to different degrees of alkyl chain surface enrichment, while interactions between the adsorbate and the anion do not play a significant role. The adsorption energy also depends on the adsorbing molecule: It decreases in the order n-butane>1-butene>iso-butane, which can be explained by different dispersion interactions.

Adsorption, Wetting, Growth, and Thermal Stability of the Protic Ionic Liquid Diethylmethylammonium Trifluoromethanesulfonate on Ag(111) and Au(111).

We have studied the adsorption, wetting, growth, and thermal evolution of the protic IL diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]) on Au(111) and Ag(111). Ultrathin films were deposited at room temperature (RT) and at 90 K, and were characterized in situ by angle-resolved X-ray photoelectron spectroscopy. For both surfaces, we observe that independent of temperature, initially, a closed 2D wetting layer forms. While the film thickness does not increase past this wetting layer at RT, at 200 K and below, "moderate" 3D island growth occurs on top of the wetting layer. Upon heating, on Au(111), the [dema][TfO] multilayers desorb at 292 K, leaving an intact [dema][TfO] wetting layer, which desorbs intact at 348 K. The behavior on Ag(111) is much more complex. Upon heating [dema][TfO] deposited at 90 K, the [dema]+ cations deprotonate in two steps at 185 and 305 K, yielding H[TfO] and volatile [dema]0. At 355 K, the formed H[TfO] wetting layer partly desorbs (∼50%) and partly decomposes to form an F-containing surface species, which is stable up to 570 K.

Enrichment effects of ionic liquid mixtures at polarized electrode interfaces monitored by potential screening.

The behavior of ionic liquids (ILs) at charged interfaces is pivotal for their application in supercapacitors and electrochemical cells. Recently, we demonstrated for neat ILs that potential screening at polarized electrode interfaces shows a characteristic voltage dependence, as determined in situ by X-ray photoelectron spectroscopy. Herein, we use this fingerprint-type behavior to characterize the nature of the IL/electrode interfaces for IL mixtures of [C8C1Im][Tf2N] and [C8C1Im]Cl on Au and Pt electrodes. For Au, the IL/electrode interfaces are dominated by the Cl- anions, even down to a 0.1 mol% [C8C1Im]Cl content. In contrast, [Tf2N]- anions enrich at the IL/Pt electrode interfaces down to 10 mol% [C8C1Im][Tf2N]; only at lower concentrations does a transition to Cl- enrichment occur. These mixture studies demonstrate that even small concentrations of another IL or contamination, e.g. remaining from synthesis, can strongly influence the situation at charged IL interfaces.

Temperature-Dependent Surface Enrichment Effects in Binary Mixtures of Fluorinated and Non-Fluorinated Ionic Liquids.

Using angle-resolved X-ray photoelectron spectroscopy (ARXPS), we investigate the topmost nanometers of various binary ionic liquid (IL) mixtures at different temperatures in the liquid state. The mixtures consist of ILs with the same [PF6 ]- anion but two different cations, namely 3-methyl-1-(3,3,4,4,4-pentafluorobutyl)imidazolium hexafluorophosphate, [PFBMIm][PF6 ], and 1-butyl-3-methylimidazolium hexafluorophosphate, [C4 C1 Im][PF6 ], with 10, 25, 50 and 75 mol % content of [PFBMIm][PF6 ]. We observe a preferential enrichment of the fluorinated chain in the topmost layer, relative to the bulk composition, which is most pronounced for the lowest content of [PFBMIm][PF6 ]. Upon cooling the mixtures stepwise from 95 °C until surface charging effects in XPS indicate solidification, we observe a pronounced increase in surface enrichment of the fluorinated chain with decreasing temperature in the liquid state. In contrast to the mixtures with lower [PFBMIm][PF6 ] contents, cooling the 75 mol % mixture additionally shows an abrupt decrease of the fluorinated chain signal before complete solidification occurs, which is assigned to partial precipitation effects.

Growth of Multilayers of Ionic Liquids on Au(111) Investigated by Atomic Force Microscopy in Ultrahigh Vacuum.

Understanding the growth of ultrathin films of ionic liquids (ILs) on metal surfaces is of highest relevance for a variety of applications. We present a detailed study of the growth of the wetting layer and successive multilayers of 1,3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C1C1Im][Tf2N]) on Au(111). By atomic force microscopy (AFM) in ultrahigh vacuum, we follow the temperature-dependent behavior between 110 and 300 K at defined coverages. We initially observe the formation of a wetting layer with a thickness of ∼0.37 nm with anions and cations arranged in a checkerboard structure. Stable AFM imaging up to 280 K allows us to follow the IL growing on top of the wetting layer in bilayers with an average thickness of ∼0.71 nm, that is, double the height of the wetting layer, in a bilayer-by-bilayer fashion. This growth behavior is independently confirmed from the surface morphology, as deduced from AFM and angle-resolved X-ray photoelectron spectroscopy. High-resolution AFM images at 110 K allow for identifying the molecular surface structure of the bilayers as a striped phase, which is one of the phases also seen for the wetting layer (Meusel, M.; Lexow, M.; Gezmis, A.; Schotz, S.; Wagner, M.; Bayer, A.; Maier, F.; Steinrück, H. P. Atomic Force and Scanning Tunneling Microscopy of Ordered Ionic Liquid Wetting Layers from 110 K up to Room Temperature. ACS Nano 2020, 14, 9000-9010).

On the adsorption of n-butane on alkyl imidazolium ionic liquids with different anions using a new molecular beam setup.

The adsorption of reactants is an elementary step in the interaction of molecules with liquid or solid surfaces. We recently reported on the trapping of n-butane on the frozen surfaces of ionic liquids (ILs), namely, 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ILs ([CnC1Im][Tf2N]; n = 1, 2, 3, and 8). To study the influence of the anion, we now present results concerning the trapping of n-butane on 1-alkyl-3-methylimidazolium hexafluorophosphate ILs ([CnC1Im][PF6]; n = 2, 4, and 8), that is, ILs with a smaller anion. The adsorption energies close to zero coverage are determined from the temperature dependence of the initial trapping probability using a novel approach. For both groups of ILs, the binding energy is dominated by the interaction of n-butane with the alkyl chain of the cation, whereas the ionic headgroups contribute only weakly. Comparing ILs with different alkyl chains at the IL cation, we find that the adsorption strength of n-butane increases with increasing length of the alkyl chain. In addition, detailed information on the new setup and the data analysis is provided.

On the Dynamic Interaction of n-Butane with Imidazolium-Based Ionic Liquids.

The impact of a reactant from the gas phase on the surface of a liquid and its transfer through this gas/liquid interface are crucial for various concepts applying ionic liquids (ILs) in catalysis. We investigated the first step of the adsorption dynamics of n-butane on a series of 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ILs ([Cn C1 Im][Tf2 N]; n=1, 2, 3, 8). Using a supersonic molecular beam in ultra-high vacuum, the trapping of n-butane on the frozen ILs was determined as a function of surface temperature, between 90 and 125 K. On the C8 - and C3 -ILs, n-butane adsorbs at 90 K with an initial trapping probability of ≈0.89. The adsorption energy increases with increasing length of the IL alkyl chain, whereas the ionic headgroups seem to interact only weakly with n-butane. The absence of adsorption on the C1 - and C2 -ILs is attributed to a too short residence time on the IL surface to form nuclei for condensation even at 90 K.

Cation Exchange at the Interfaces of Ultrathin Films of Fluorous Ionic Liquids on Ag(111).

In the context of applications with thin ionic liquid (IL) films on solid supports, we studied the ion distribution within mixed thin IL films by angle-resolved X-ray photoelectron spectroscopy. After the deposition of 1-methyl-3-octylimidazolium hexafluorophosphate, [C8C1Im][PF6], on top of a wetting layer (WL) of 3-methyl-1-(3,3,4,4,4-pentafluorobutyl)imidazolium hexafluorophosphate, [PFBMIm][PF6], on Ag(111) at room temperature (RT), we find a preferential enrichment of the [PFBMIm]+ cation at the IL/vacuum interface. In a similar deposition experiment at 82 K, this cation exchange at the IL/solid interface does not occur. Upon heating the film from 82 K to RT, we observe the replacement of [C8C1Im]+ by [PFBMIm]+ at the IL/vacuum interface between ∼160 and ∼220 K. No further changes in the surface composition were observed between 220 K and RT. Upon further heating the mixed IL film, we find the complete desorption of [PFBMIm][PF6] from the mixed film below 410 K, leaving a WL of pure [C8C1Im][PF6] on Ag(111), which desorbs until 455 K.

Wave-CAIPI for highly accelerated MP-RAGE imaging.

PURPOSE: To introduce a highly accelerated T1-weighted magnetization-prepared rapid gradient echo (MP-RAGE) acquisition that uses wave-controlled aliasing in parallel imaging (wave-CAIPI) encoding to retain high image quality. METHODS: Significant acceleration of the MP-RAGE sequence is demonstrated using the wave-CAIPI technique. Here, sinusoidal waveforms are used to spread aliasing in all three directions to improve the g-factor. Combined with a rapid (2 s) coil sensitivity acquisition and data-driven trajectory calibration, we propose an online integrated acquisition-reconstruction pipeline for highly efficient MP-RAGE imaging. RESULTS: The 9-fold accelerated MP-RAGE acquisition can be performed in 71 s, with a maximum and average g-factor of gmax = 1.27 and gavg = 1.06 at 3T. Compared with the state-of-the-art method controlled aliasing in parallel imaging results in higher acceleration (2D-CAIPIRINHA), this is a factor of 4.6/1.4 improvement in gmax /gavg . In addition, we demonstrate a 57 s acquisition at 7T with 12-fold acceleration. This acquisition has a g-factor performance of gmax = 1.15 and gavg = 1.04. CONCLUSION: Wave encoding overcomes the g-factor noise amplification penalty and allows for an order of magnitude acceleration of MP-RAGE acquisitions. Magn Reson Med 79:401-406, 2018. © 2017 International Society for Magnetic Resonance in Medicine.